Portable tri-color ratiometric fluorescence paper sensor for intelligent visual detection of dual-antibiotics and aluminium ion.

The toxicological effect between co-existed antibiotics and metal ions was dangerous to the ecological environment and public health. However, the rapid quantification tools with convenience, accuracy and low cost for the detection of multiple targets were still challenging. Herein, a portable tri-color ratiometric fluorescence paper sensor was constructed by coupling of blue carbon dots and fluorescence imprinted polymer for down/up conversion simultaneous detection of tetracycline and sulfamethazine. Interestingly, the cascade detection of aluminum ion was also realized based on the individual detection system of tetracycline without the assistance of complex coupling reagents. The detection limits of smartphone method for the visual detection of tetracycline, sulfamethazine and aluminum ion were calculated as 0.014 µM, 0.004 µM and 0.019 µM, respectively. The portable fluorescence paper sensor was applied for the visual detection of tetracycline, sulfamethazine and aluminum ion in actual samples successfully with satisfactory recoveries. With the advantages of rapidness, low cost, and portability, the developed portable fluorescence paper sensor provided a new strategy for the visual real-time detection of multiple targets.

Isolation, identification and whole-genome analysis of an Achromobacter strain with a novel sulfamethazine resistance gene and sulfamethazine degradation gene cluster.

A sulfamethazine (SM2) degrading strain, Achromobacter mucicolens JD417, was isolated from sulfonamide-contaminated sludge using gradient acclimation. Optimal SM2 degradation conditions were pH 7, 36 °C, and 5 % inoculum, achieving a theoretical maximum degradation rate of 48 % at 50 ppm SM2. Cell growth followed the Haldane equation across different SM2 concentrations. Whole-genome sequencing of the strain revealed novel functional annotations, including a sulfonamide resistance gene (sul4) encoding dihydropteroate synthase, two flavin-dependent monooxygenase genes (sadA and sadB) crucial for SM2 degradation, and unique genomic islands related to metabolism, pathogenicity, and resistance. Comparative genomics analysis showed good collinearity and homology with other Achromobacter species exhibiting organics resistance or degradation capabilities. This study reveals the novel molecular resistance and degradation mechanisms and genetic evolution of an SM2-degrading strain, providing insights into the bioremediation of sulfonamide-contaminated environments.

Photo-thermal activation of persulfate for the efficient degradation of synthetic and real industrial wastewaters: System optimization and cost estimation.

The photo-thermal activation of persulfate (PS) was carried out to degrade various pollutants such as reactive blue-222 (RB-222) dye, sulfamethazine, and atrazine. Optimizing the operating parameters showed that using 0.90 g/L of PS at pH 7, temperature of 90 °C, initial dye concentration of 21.60 mg/L, and reaction time of 120 min could attain a removal efficiency of 99.30%. The degradation mechanism was explored indicating that hydroxyl and sulfate radicals were the prevailing reactive species. The degradation percentages of 10 mg/L of sulfamethazine and atrazine were 83.30% and 70.60%, respectively, whereas the mineralization ratio was 63.50% in the case of real textile wastewater under the optimal conditions at a reaction time of 120 min. The treatment cost per 1 m3 of real wastewater was appraised to be 1.13 $/m3 which assured the inexpensiveness of the proposed treatment system. This study presents an effective and low-cost treatment system that can be implemented on an industrial scale.

Reduced sulfur accelerates Fe(III)/Fe(II) recycling in FeS2 surface for enhanced electro-Fenton reaction.

FeS2 is well-known for its role in redox reactions. However, the mechanism within heterogeneous electron-Fenton (Hetero-EF) systems remains unclear. In this study, a novel FeS2 based three-dimensional system (GF/Cu-FeS2) with self-generation of H2O2 was investigated for Hetero-EF degradation of sulfamethazine (SMZ). The results revealed that SMZ could be completely removed in 1.5 h, accompanying with the mineralization efficiency of 96% within 4 h. This system performed excellent stability, evidenced by consistently eliminated 100% of SMZ within 2 h over 4 cycles. The generated Reactive Oxygen Species (ROS) of •OH and •O2- in every degradation cycle were quantitatively measured to confirm the stability of the GF/Cu-FeS2 system. Additionally, the redox reaction mechanism on the surface of FeS2 was thoroughly analyzed in detail. The accelerated reduction of Fe(III) to Fe(II), triggered by S22- on the surface of FeS2, promoted the iron cycling, thereby quickening the Fenton process. Density Functional Theory (DFT) results illustrated the process of S22- to be oxidized to in detail. Therefore, this work provides deeper insight into the mechanistic role of S22- in FeS2 for environmental remediation.

Carrageenan derived polyelectrolyte complexes material: An effective bifunctional for electrochemical sensing of sulfamethazine and antibacterial activity.

Biopolymer-derived polyelectrolyte complexes (PECs) are a class of materials that have emerged as promising candidates for developing advanced electrochemical sensors due to their tunable properties, biocompatibility, cost-effective production, and high surface area. PECs are formed by combining positively and negatively charged polymers, resulting in a network with intriguing properties that can be tailored for specific sensing applications. The resultant PECs-based nanocomposites were used to modify the glassy carbon electrode (GCE) to detect the sulfamethazine (SFZ) antibiotic drug. In addition, electrochemical studies using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and differential pulse voltammetry (DPV) are used to evaluate the SFZ detection ability. Similarly, various microscopic and spectroscopic studies investigated the nano composite's structural features and morphological behavior. The κ-CGN/P(Am-co-DMDAAc)-GO modified GCE demonstrated excellent detection ability of SFZ with the nano molar range and without interference with similar structural components. Furthermore, the newly fabricated electrode κ-CGN/P(Am-co-DMDAAc)-GO was derived from naturally available materials, water-soluble, low cost, biocompatible, exhibits good conductivity, and excellent catalytic properties. Finally, κ-CGN/P(Am-co-DMDAAc)-GO- modified GCE has versatile, practical applications for detecting SFZ in real-time samples and determining the efficacy of an antibacterial activity.

A recyclable SERS-DGT device for in-situ sensing of sulfamethazine by Au@g-C3N4NS in water.

Although diffusion gradient in thin-film technique (DGT) has realized the in-situ sampling Sulfamethazine (SMT), the traditional DGT devices cannot be served as sensing devices but in-situ sampling devices. Here we report a recyclable surface enhanced Raman scattering (SERS) responsive DGT sensing device (recyclable SERS-DGT Sensing Device) capable of in-situ sensing of SMT in water. This is achieved by innovatively utilizing a recyclable SERS responsive liquid suspension of Au nanoparticles supported on g-C3N4 (Au@g-C3N4NS) as DGT binding phase. Au@g-C3N4NS is synthesized via in-situ growth method and embed in DGT binding phase, which exhibits good SERS activity, aqueous stability recyclable and adsorption performance. The SERS-DGT Sensing Device is valid for measuring SMT under a wide range of conditions (i.e., deployment time 24∼180 h, concentrations range of 1.031∼761.9 ng mL-1, pH 5∼9, ionic strength 0.0001∼0.05 mol L-1 NaCl, DOM concentrations 0∼100 mg L-1, four recycles). Furthermore, substrate combined with DGT binding phase, can integrate the sampling, pretreatment and SERS detection of SMT, which can be recycled, improving the reliability and efficiency of environmental monitoring. In this article, recyclable SERS-DGT Sensing Device, a platform for recyclable in-situ sensing of antibiotics, holds great potential for environmental monitoring.

Manure application amplified the co-selection of quaternary ammonium disinfectant and antibiotic on soil antibiotic resistome.

Disinfectants and antibiotics are widely used for the prevention and control of bacterial infectious diseases. Frequent disinfection is thought to exacerbate antibiotic resistance. However, little is known about how disinfectants and antibiotics co-induce changes in the soil antibiotic resistance genes (ARGs). This study determined the ARG profiles and bacterial community dynamics between unamended soil and manure-amended soil exposed to benzalkonium chloride (C12) (BC, 10 mg kg-1) disinfectant and sulfamethazine (SMZ, 1 mg kg-1), using high-throughput quantitative PCR and 16 S rRNA gene sequencing. Manure application enriched the soil in terms of ARGs abundance and diversity, which synergistically amplified the co-selection effect of BC and SMZ on soil antibiotic resistome. Compared with the control treatment, BC and SMZ exposure had a smaller impact on the bacterial infectious diseases and antimicrobial resistance-related functions in manure-amended soil, in which bacterial communities with greater tolerance to antimicrobial substances were constructed. Manure application increased the proportion of rank I ARGs and potential human pathogenic bacteria, while BC and SMZ exposure increased the drug-resistant pathogens transmission risk. This study validated that BC and SMZ aggravated the antimicrobial resistance under manure application, providing a reference for managing the spread risk of antimicrobial resistance in agricultural activities.

Antimicrobials in Eisenia fetida earthworms: A comprehensive study from method development to the assessment of uptake and degradation.

In this work, an accurate analytical method was developed for the simultaneous analysis of twenty-seven antimicrobials (AMs) in earthworms using liquid chromatography coupled to a triple quadrupole mass spectrometry detector (UHPLC-MS/MS). Adequate apparent recoveries (80-120 %) and limits of quantification (LOQ) (1 µg·kg-1 - 10 µg·kg-1) were obtained, with the exception of norfloxacin (34 µg·kg-1). The method was applied to evaluate the accumulation of sulfamethazine (SMZ) and tetracycline (TC) in earthworms after performing OECD-207 toxicity test, in which Eisenia fetida (E. fetida) organisms were exposed to soils spiked with 10 mg·kg-1, 100 mg·kg-1 or 1000 mg·kg-1 of SMZ and TC, individually. The results confirmed the bioaccumulation of both AMs in the organisms, showing a greater tendency to accumulate SMZ since higher bioconcentration factor values were obtained for this compound at the exposure concentrations tested. In addition, the degradation of both AMs in both matrices, soils and earthworms was studied using liquid chromatography coupled to a q-Orbitrap high resolution mass spectrometry detector. Thirteen transformation products (TPs) were successfully identified, eight of them being identified for the first time in soil/earthworm (such as 4-Amino-3-chloro-n-(4,6-dimethylpyrimidin-2-yl)benzenesulfonamide or 4-(dimethylamino)-1,11,12a-trihydroxy-6,6-dimethyl-3,7,10,12-tetraoxo-3,4,4a,5,5a,6,7,10,12,12a-decahydrotetracene-2-carboxamide, among others) and their formation/degradation trend over time was also studied. Regarding the biological effects, only SMZ caused changes in earthworm growth, evidenced by weight loss in earthworms exposed to concentrations of 100 mg·kg-1 and 1000 mg·kg-1. Riboflavin decreased at all concentrations of SMZ, as well as at the highest concentration of TC. This indicates that these antibiotics can potentially alter the immune system of E. fetida. This research represents a significant advance in improving our knowledge about the contamination of soil by AM over time. It investigates the various ways in which earthworms are exposed to AMs, either by skin contact or ingestion. Furthermore, it explores how these substances accumulate in earthworms, the processes by which earthworms break them down or metabolise them, as well as the resulting TPs. Finally, it examines the potential effects of these substances on the environment.

Degradation of sulfamethazine by microbial electrolysis cell with nickel-cobalt co-modified biocathode.

In this study, nickel-cobalt co-modified stainless steel mesh (Ni-Co@SSM) was prepared and used as the biocathode in microbial electrolysis cell (MEC) for sulfamethazine (SMT) degradation. The optimal electrochemical performance of the Ni-Co@SSM was obtained at the electrodeposition time of 600 s, electrodeposition current density of 20 mA cm-2, and nickel-cobalt molar ratio of 1:2. The removal of SMT in MEC with the Ni-Co@SSM biocathode (MEC-Ni-Co@SSM) was 82%, which increased by 30% compared with the conventional anaerobic reactor. Thirteen intermediates were identified and the potential degradation pathways of SMT were proposed. Proteobacteria, Firmicutes, Patescibacteria, Chloroflexi, Bacteroidetes, and Euryarchaeota are the dominant bacteria at the phylum level in the MEC-Ni-Co@SSM, which are responsible for SMT metabolism. Due to the electrical stimulation, there was an increase in the abundance of the metabolic function and the genetic information processing. This work provides valuable insight into utilizing MECs for effective treatment of antibiotic-containing wastewater.

Adsorption of antibiotics onto low-grade charcoal in the presence of organic matter: Batch and column tests.

Antibiotics contaminate diverse ecosystems and threaten human health. In ecosystems including water, sediment, and soil, the amount of antibiotics present is tiny compared to the amount of natural organic matter. However, most studies have ignored the co-presence of natural organic matter in the adsorption of target antibiotics. In this study, we quantitatively evaluated the effect of co-presenting natural organic matter on the adsorption of sulfamethazine (SMZ) through batch and column experiments using low-grade charcoal, an industrial by-product. SMZ was used as a model antibiotic compound and humic acid (HA) was used to represent natural organic matter. The co-presence of 2000 mg/L HA (400 times the concentration of SMZ) lowered the adsorption rate of SMZ from 0.023 g/mg·min to 0.007 g/mg·min, and the maximum adsorption capacity from 39.8 mg/g to 15.6 mg/g. HA blocked the charcoal's pores and covered its surface adsorption sites, which dramatically lowered its capacity to adsorb SMZ. Similar results were obtained in the flow-through column experiments, where the co-presence of natural organic matter shortened the lifetime of the charcoal. As a result, the co-presence of a relatively high concentration of natural organic matter can inhibit the adsorption of SMZ and likely other antibiotic compounds, and thus the presence of natural organic matter should be accounted for in the design of adsorption processes to treat antibiotics in water.

Degradation kinetics of veterinary antibiotics and estrogenic hormones in a claypan soil.

Veterinary antibiotics and estrogens are excreted in livestock waste before being applied to agricultural lands as fertilizer, resulting in contamination of soil and adjacent waterways. The objectives of this study were to 1) investigate the degradation kinetics of the VAs sulfamethazine and lincomycin and the estrogens estrone and 17ß-estradiol in soil mesocosms, and 2) assess the effect of the phytochemical DIBOA-Glu, secreted in eastern gamagrass (Tripsacum dactyloides) roots, on antibiotic degradation due to the ability of DIBOA-Glu to facilitate hydrolysis of atrazine in solution assays. Mesocosm soil was a silt loam representing a typical claypan soil in portions of Missouri and the Central United States. Mesocosms (n = 133) were treated with a single target compound (antibiotic concentrations at 125 ng g-1 dw, estrogen concentrations at 1250 ng g-1 dw); a subset of mesocosms treated with antibiotics were also treated with DIBOA-Glu (12,500 ng g-1 dw); all mesocosms were kept at 60% water-filled pore space and incubated at 25 °C in darkness. Randomly chosen mesocosms were destructively sampled in triplicate for up to 96 days. All targeted compounds followed pseudo first-order degradation kinetics in soil. The soil half-life (t0.5) of sulfamethazine ranged between 17.8 and 30.1 d and ranged between 9.37 and 9.90 d for lincomycin. The antibiotics results showed no significant differences in degradation kinetics between treatments with or without DIBOA-Glu. For estrogens, degradation rates of estrone (t0.5 = 4.71-6.08 d) and 17ß-estradiol (t0.5 = 5.59-6.03 d) were very similar; however, results showed that estrone was present as a metabolite in the 17ß-estradiol treated mesocosms and vice-versa within 24 h. The antibiotics results suggest that sulfamethazine has a greater potential to persist in soil than lincomycin. The interconversion of 17ß-estradiol and estrone in soil increased their overall persistence and sustained soil estrogenicity. This study demonstrates the persistence of these compounds in a typical claypan soil representing portions of the Central United States.

Degradation of sulfonamide antibiotic via UV/MgO2 system: kinetic, application, and mechanism.

In response to antibiotic residues in the water, a novel advanced oxidation technology based on MgO2 was used to remediate sulfamethazine (SMTZ) pollution in aquatic environments. Upon appropriate regulation, the remarkable removal efficiency of SMTZ was observed in a UV/MgO2 system, and the pseudo-first-order reaction constant reached 0.4074 min-1. In addition, the better performance of the UV/MgO2 system in a weak acid environment was discovered. During the removal of SMTZ, the pathways of SMTZ degradation were deduced, including nitration, ring opening, and group loss. In the mineralization exploration, the further removal of residual products of SMTZ by the UV/MgO2 system was visually demonstrated. The qualitative and quantitative researches as well as the roles of reactive species were valuated, which revealed the important role of ·O2-. Common co-existing substances in actual wastewater such as NO3- HA, Cl-, Fe2+, Co2+, and Mn2+ can slightly inhibit the degradation of SMTZ in the UV/MgO2 system. Finally, the capacity of efficient degradation of SMTZ in actual wastewater by the UV/MgO2 system was proved. The results indicated that the innovative UV/MgO2 system was of great practical application prospect in antibiotic residue wastewater remediation.

Surface functional groups on nanoplastics delay the recovery of gut microbiota after combined exposure to sulfamethazine in marine medaka (Oryzias melastigma).

Nanoplastics can interact with antibiotics, altering their bioavailability and the ensuing toxicity in marine organisms. It is reported that plain polystyrene (PS) nanoplastics decrease the bioavailability and adverse effects of sulfamethazine (SMZ) on the gut microbiota in Oryzias melastigma. However, the influence of surface functional groups on the combined effects with SMZ remains largely unknown. In this study, adult O. melastigma were fed diet amended with 4.62 mg/g SMZ and 3.65 mg/g nanoplastics (i.e., plain PS, PS-COOH and PS-NH2) for 30 days (F0-E), followed by a depuration period of 21 days (F0-D). In addition, the eggs produced on the last day of exposure were cultured under standard protocols without further exposure for 2 months (F1 fish). The results showed that the alpha diversity or the bacterial community of gut microbiota did not differ among the SMZ + PS, SMZ + PS-COOH, and SMZ + PS-NH2 groups in the F0-E and F1 fish. Interestingly, during the depuration, a clear recovery of gut microbiota (e.g., increases in the alpha diversity, beneficial bacteria abundances and network complexity) was found in the SMZ + PS group, but not for the SMZ + PS-COOH and SMZ + PS-NH2 groups, indicating that PS-COOH and PS-NH2 could prolong the toxic effect of SMZ and hinder the recovery of gut microbiota. Compared to plain PS, lower egestion rates of PS-COOH and PS-NH2 were observed in O. melastigma. In addition, under the simulated fish digest conditions, the SMZ-loaded PS-NH2 was found to desorb more SMZ than the loaded PS and PS-COOH. These results suggested that the surface -COOH and -NH2 groups on PS could influence their egestion efficiency and the adsorption/desorption behavior with SMZ, resulting in a long-lasting SMZ stress in the gut during the depuration phase. Our findings highlight the complexity of the carrier effect and ecological risk of surface-charged nanoplastics and the interactions between nanoplastics and antibiotics in natural environments.

Development and validation of method for the simultaneous determination of sulfamethazine, trimethoprim and doxycycline in veterinary formulation using high performance liquid chromatography.

Sulfamethazine (SMZ), trimethoprim (TMP) and doxycycline (DOXY) are drugs of choice used in the treatment of intestinal and respiratory infections that affect poultry and swine. The aim of this study was develop and validate a simple, sensitive and fast method for the simultaneous determination of SMZ, TMP and DOXY in veterinary formulations by high-performance liquid chromatography. The separation was performed on a Macherey-Nagel C8 analytical column (4 × 125 mm, 5 µm), with a flow rate of 0.5 ml min-1 and detection at 268, 270 and 350 nm, for SMZ, TMP and DOXY, respectively. All measurements were performed in acetonitrile-water (45:55 v/v; pH 3.0). The analytical curves were linear (r > 0.9997) in the concentration range of 5.0-35.0 µg ml-1 for SMZ, 1.0-7.0 µg ml-1 for TMP and 7.0-13.0 µg ml-1 for DOXY. The method proved to be precise, robust, accurate and selective. In accelerated stability, the sample was analyzed for 6 months, with no major variations observed in organoleptic analysis and pH. Therefore, the developed method was proved to be suitable for routine quality control analyses for the simultaneous determination of SMZ, TMP and DOXY in pharmaceutical formulations.

Detection of Multiple Antibiotic Residues in Turkish Pine and Blossom Honeys Using LC-MS/MS Method.

Due to the high demand for honey, beekeepers often feed the bees with antibiotics to protect honeybees against illnesses; the determination of veterinary drugs and their residues in bee products especially in honey is gaining importance. In this study, commercially available 15 different brands, a total of 22 honey (14 blossoms and 8 pines) samples obtained from 5 chain supermarkets in the city of Bingöl and Diyarbakir, Turkey were analysed for 29 antibiotic residues. These antibiotics belong to 10 different categories, including tetracyclines, aminoglycosides, macrolides, sulfonamides, fluoroquinolones, benzimidazoles, anthelmintic, amphenicols, quinolines, and oxazolidines. For the qualitative and quantitative determination of the antibiotics, a triple quadrupole liquid chromatography-tandem mass spectrometry (LC-MS/MS) was used. A total of 10 out of 22 honey (8 blossom, 57.14 % and 2 pine, 25 %) samples were found to be positive for antibiotics. Among the tested antibiotics, tetracycline, dihydrostreptomycin, streptomycin, erythromycin, and sulfadimidine were detected in the honey samples. Dihydrostreptomycin and sulfadimidine were detected in 6 samples, erythromycin was determined in 4 samples, streptomycin was found in 2 samples, and lastly, tetracycline was detected only in one sample. The highest and the lowest concentrations of antibiotics detected in the samples were dihydrostreptomycin and erythromycin found at the amount of 992.58 µg/kg and 0.77 µg/kg respectively. The proposed method was validated with a limit of quantification (LOQ) and limit of detection (LOD) ranging between 0.42 and 3.22 µg /kg and 0.13-0.97 µg /kg respectively. Good linearities were also achieved ranging between R2 =0.987 and 0.999.

Identification of sulfamethazine degraders in swine farm-impacted river and farmland: A comparative study of aerobic and anaerobic environments.

Sulfonamides (SAs) are extensively used antibiotics in the prevention and treatment of animal diseases, leading to significant SAs pollution in surrounding environments. Microbial degradation has been proposed as a crucial mechanism for removing SAs, but the taxonomic identification of microbial functional guilds responsible for SAs degradation in nature remain largely unexplored. Here, we employed 13C-sulfamethazine (SMZ)-based DNA-stable isotope probing (SIP) and metagenomic sequencing to investigate SMZ degraders in three distinct swine farm wastewater-receiving environments within an agricultural ecosystem. These environments include the aerobic riparian wetland soil, agricultural soil, and anaerobic river sediment. SMZ mineralization activities exhibited significant variation, with the highest rate observed in aerobic riparian wetland soil. SMZ had a substantial impact on the microbial community compositions across all samples. DNA-SIP analysis demonstrated that Thiobacillus, Auicella, Sphingomonas, and Rhodobacter were dominant active SMZ degraders in the wetland soil, whereas Ellin6067, Ilumatobacter, Dongia, and Steroidobacter predominated in the agricultural soil. The genus MND1 and family Vicinamibacteraceae were identified as SMZ degrader in both soils. In contrast, anaerobic SMZ degradation in the river sediment was mainly performed by genera Microvirga, Flavobacterium, Dechlorobacter, Atopostipes, and families Nocardioidaceae, Micrococcaceae, Anaerolineaceae. Metagenomic analysis of 13C-DNA identified key SAs degradation genes (sadA and sadC), and various of dioxygenases, and aromatic hydrocarbon degradation-related functional genes, indicating their involvement in degradation of SMZ and its intermediate products. These findings highlight the variations of indigenous SAs oxidizers in complex natural habitats and emphasize the consideration of applying these naturally active degraders in future antibiotic bioremediation.

Ascorbic acid promoted sulfadimidine degradation in the magnetite-activated persulfate system by facilitating the Fe(III)/Fe(II) cycle.

Persulfate (PS) activation technologies were of significant importance to the organic contaminant treatment. In this study, ascorbic acid (AA) was introduced to the traditional PS-activated process by using magnetite (Fe3O4) as the activator; herein, the degradation efficiency of sulfadimidine (SM2) was improved from 30 to 93% within 3 h, and the observed removal rate was about 8.0 times higher than that of the Fe3O4/PS system. These improvements were found to be induced by the added AA because it could reduce the surface Fe(III) to Fe(II) on Fe3O4 and thus facilitate the Fe(III)/Fe(II) cycle, which was conducive to producing reactive oxygen species (ROSs) in the oxidation process during PS activation. Meanwhile, AA could also promote the Fe(III)/Fe(II) cycle in the homogeneous solution, further advancing the PS decomposition for SM2 degradation. The ROS trapping experiments indicated that SM2 removal in the Fe3O4/PS/AA system was attributed to •OH and •SO4-, and •SO4- was the dominant ROS. Moreover, the reusability test experiment revealed that magnetite retained good activity after five cycles in the Fe3O4/AA/PS system. This study provides a promising PS activation technology for efficient organics contaminant treatment.

[Effect of Manure Application on the Adsorption of Antibiotics to Soil].

Sulfonamide antibiotics and florfenicol(FFC) are commonly used antibiotics in Zhejiang Province. They have weak adsorption on soil and are easy to migrate, with high environmental risks. In recent years, most of the studies on the potential risk of fecal-derived antibiotics to farmland soil were conducted by adding manure under laboratory conditions; therefore, it is impossible to assess the risk of antibiotic pollution under natural fertilization. Therefore, batch balance experiments were conducted to explore the effects of different soil types and manure types on the adsorption of antibiotics in the soil, in which five types of dryland farmland soils[Lin'an(LA), Jiashan(JS), Longyou(LY), Kaihua(KH), and Jinhua(JH)]in Zhejiang Province that have been used with different fertilizers(chicken manure, pig manure, and chemical fertilizer) for a long time were chosen, and four types of commonly used antibiotics[sulfadiazine(SD), sulfamethazine(SMT), sulfamethoxazole(SMZ), and FFC]were selected. The results showed that the adsorption of the four antibiotics in the experimental soil was weak, and the adsorption capacity decreased in the order of:SMT(1.44-13.23 mg1-(1/n)·L1/n·kg-1)>SMZ(0.73-6.05 mg1-(1/n)·L1/n·kg-1)>SD(0.16-5.57 mg1-(1/n)·L1/n·kg-1)>FFC(0.27-3.81 mg1-(1/n)·L1/n·kg-1). The Freundlich model was superior to the linear model in fitting the isotherm adsorption of SD, SMT, and FFC, in which SD and FFC belonged to "S" type adsorption, and SMT belonged to "L" type adsorption. For SMZ, the fitting effect of the linear model was better than that of the Freundlich model. The contents of total organic carbon(TOC) and dissolved organic carbon(DOC) could better predict the adsorption capacity of the four antibiotics(r=0.548-0.808), and the values of cation exchange capacity(CEC) and electrical conductivity(EC) could better predict the adsorption capacity of SMT and FFC(r=0.758-0.841). Compared with the application of chemical fertilizer, manure application increased the values of TOC, DOC, CEC, and EC in acidic and neutral soils, which was conducive to the adsorption of antibiotics on the soil. Meanwhile, manure application also increased pH in acidic and neutral soils, which was not conducive to the adsorption of antibiotics on the soil. In addition, manure application reduced the values of TOC, DOC, CEC, EC, and pH in alkaline soils. The lower pH was conducive to antibiotic adsorption on the soil, whereas the lower content of the other four was not conducive to antibiotic adsorption on the soil. For the acidic soil with low fertility, the application of manure increased soil fertility and thus increased the adsorption of antibiotics on the soil, such as the LA soil with chicken manure, the LY(1) soil with pig manure, and the JH soil with chicken manure and pig manure. However, for the acidic and neutral soils with high fertility, the application of manure had significantly increased soil pH and thus reduced the adsorption of antibiotics on the soil, such as the JS soil with chicken manure and pig manure and the LY(2) soil with chicken manure. For calcareous soil with high fertility and pH(such as KH soil), the adsorption profiles of the four types of antibiotics on the soil showed diversity after the application of manure:the adsorption capacity of SD increased significantly after the application of chicken manure and pig manure, whereas the adsorption capacity of SMT and SMZ decreased significantly, and the adsorption capacity of FFC declined significantly after the application of chicken manure. Therefore, manure application according to soil fertility could effectively control the environmental risk of fecal antibiotics.

Dietary exposure to sulfamethazine alters fish intestinal homeostasis and promotes resistance gene transfer.

The present study was undertaken to explore the effects of sulfamethazine (SMZ) dietary exposure on the enrichment of the intestine microbial structure, and antibiotic resistance gene (ARGs) transmission in marine medaka, with respect to antibiotic dose, duration, and sex. In male fish, a dietary exposure of 10 µg/L SMZ led to a heightened SMZ enrichment in the intestine, whereas metabolite (N-SMZ) levels were elevated at a higher exposure concentration (100 µg/L). Conversely, female fish exhibited stable levels of accumulation and metabolic rates across the exposure period. The composition of intestinal microorganisms revealed that exposure duration exerted a greater impact on the abundance and diversity of gut microbes, and microbial responses to SMZ varied across exposure time points. The expansion of Bacteroidetes and Ruegeria likely stimulated SMZ metabolism and contributed to the more balanced level of SMZ and N-SMZ observed in females. In males, short-term SMZ stress resulted in a disruption of intestinal homeostasis, while the rise in the abundance of the Fusobacteria and Propionigeniuma suggested a potential enhancement in intestinal anti-inflammatory capacity over time. Overall, female medaka exhibited greater adaptability to SMZ, and males appear to experience prolonged effects due to SMZ. A total of 11 ARGs and 5 mobile genetic elements (MGEs) were identified. Ruegeria is the main carrier of two types of MGEs (IS1247, ISSm2-Xanthob), and may serve as an indicator of ARG transmission. Therefore, it is rational to consider some fish breeding areas in natural waters as potential "reservoirs" of antibiotic resistance. This research will provide a valuable reference for the transmission of drug resistance along the food chain.

Copper regulates degradation of typical antibiotics by microalgal-fungal consortium in simulated swine wastewater: insights into metabolic routes and dissolved organic matters.

Microalgae-based biotechnology for antibiotics biodegradation in swine wastewater has been receiving an increasing attention. In this study, microalgae and fungi co-cultivation system, regulated by copper (Cu(II)), was investigated in terms of nutrients and sulfonamides degradation in simulated swine wastewater. Results showed that the removal of ammonium nitrogen (NH4+-N), total nitrogen (TN), total phosphorus (TP) and chemical oxygen demand (COD) by microalgal-fungal consortium increased under 0.1-0.5 mg/L Cu(II) with the highest removal efficiency of 79.19%, 76.18%, 93.93% and 93.46%, respectively. The addition of Cu(II) (0-0.5 mg/L) enhanced the removal of sulfamonomethoxine (SMM), sulfamethoxazole (SMX) and sulfamethazine (SMZ) from 49.05% to 58.76%, from 59.31% to 63.51%, and from 37.51% to 63.9%, respectively, and the main removal mechanism was found to be biodegradation. Biodegradation followed a pseudo-first-order model with variable half-lives (10.12 to 15.51 days for SMM, 9.01 to 10.88 days for SMX, and 8.74 to 12.85 days for SMZ). Through mass spectrometry analysis, metabolites and intermediates of sulfonamides were accordingly identified, suggesting that the degradation routes were involved with hydroxylation, deamination, oxidation, de-sulfonation and bond cleavage. Dissolved organic matters released by microalgal-fungal consortium were induced by Cu(II). Fulvic acid-like and protein-like substances were bound to Cu(II), reducing its concentration and thus mitigating the organismal damage to microorganisms. These findings drew an insightful understanding of microalgal-fungal consortium for sulfonamides remediation by Cu(II) regulation in simulated swine wastewater.