Serotype diversity and antimicrobial susceptibility profiles of Actinobacillus pleuropneumoniae isolated in Italian pig farms from 2015 to 2022.

Actinobacillus pleuropneumoniae (APP) is a bacterium frequently associated with porcine pleuropneumonia. The acute form of the disease is highly contagious and often fatal, resulting in significant economic losses for pig farmers. Serotype diversity and antimicrobial resistance (AMR) of APP strains circulating in north Italian farms from 2015 to 2022 were evaluated retrospectively to investigate APP epidemiology in the area. A total of 572 strains isolated from outbreaks occurring in 337 different swine farms were analysed. The majority of isolates belonged to serotypes 9/11 (39.2%) and 2 (28.1%) and serotype diversity increased during the study period, up to nine different serotypes isolated in 2022. The most common resistances were against tetracycline (53% of isolates) and ampicillin (33%), followed by enrofloxacin, florfenicol and trimethoprim/sulfamethoxazole (23% each). Multidrug resistance (MDR) was common, with a third of isolates showing resistance to more than three antimicrobial classes. Resistance to the different classes and MDR varied significantly depending on the serotype. In particular, the widespread serotype 9/11 was strongly associated with florfenicol and enrofloxacin resistance and showed the highest proportion of MDR isolates. Serotype 5, although less common, showed instead a concerning proportion of trimethoprim/sulfamethoxazole resistance. Our results highlight how the typing of circulating serotypes and the analysis of their antimicrobial susceptibility profile are crucial to effectively manage APP infection and improve antimicrobial stewardship.

Photocatalytic degradation process of antibiotic sulfamethoxazole by ZnO in aquatic systems: a dynamic kinetic model based on contributions of OH radical, oxygenated radical intermediates and dissolved oxygen.

The photocatalytic degradation process of sulfamethoxazole (SMX) using ZnO in aquatic systems has been systematically studied by varying initial SMX concentration from 0 to 15 mgL-1, ZnO dosage from 0 to 4 gL-1 and UV light intensity at the light source from 0 to 18 W(m-lamp length)-1 at natural pH. Almost complete degradations of SMX were achieved within 120 min for the initial SMX concentration ≤15 mgL-1 with ZnO dosage of 3 gL-1 and UV light intensity of 18 W(m-lamp length)-1. The photocatalytic degradation process was found to be interacted with the dissolved oxygen (DO) consumption. With oxygen supply through the gas-liquid free-surface, the DO concentration decreased significantly in the initial SMX degradation phase and increased asymptotically to the saturated DO concentration after achieving about 80% SMX degradation. The change in DO concentration was probably controlled by the oxygen consumption in the formation of oxygenated radical intermediates. A novel dynamic kinetic model based on the fundamental reactions of photocatalysis and the formation of oxygenated radical intermediates was developed. In the modeling the dynamic concentration profiles of OH radical and DO are considered. The dynamics of SMX degradation process by ZnO was simulated reasonably by the proposed model.

Silver Nanoparticle-Embedded Hydrogels for Electrochemical Sensing of Sulfamethoxazole Residues in Meat.

A disposable electrochemical sensor based on silver nanoparticle-embedded cellulose hydrogel composites was developed for sensitive detection of sulfamethoxazole residues in meat samples. Scanning electron microscopy confirmed the porous structure of the cellulose matrix anchored with 20-50 nm silver nanoparticles (AgNPs). Fourier transform infrared spectroscopy and X-ray diffraction verified that the metallic AgNPs coordinated with the amorphous cellulose chains. At an optimum 0.5% loading, the nanocomposite sensor showed a peak-to-peak separation of 150 mV, diffusion-controlled charge transfer kinetics, and an electron transfer coefficient of 0.6 using a ferro/ferricyanide redox probe. Square-wave voltammetry was applied for sensing sulfamethoxazole based on its two-electron oxidation peak at 0.72 V vs. Ag/AgCl in Britton-Robinson buffer of pH 7.0. A linear detection range of 0.1-100 µM sulfamethoxazole was obtained with a sensitivity of 0.752 µA/µM and limit of detection of 0.04 µM. Successful recovery between 86 and 92% and less than 6% RSD was achieved from spiked meat samples. The key benefits of the proposed disposable sensor include facile fabrication, an antifouling surface, and a reliable quantification ability, meeting regulatory limits. This research demonstrates the potential of novel cellulose-silver nanocomposite materials towards developing rapid, low-cost electroanalytical devices for decentralized on-site screening of veterinary drug residues to ensure food safety.

Sulfur Vacancies in Pyrite Trigger the Path to Nonradical Singlet Oxygen and Spontaneous Sulfamethoxazole Degradation: Unveiling the Hidden Potential in Sediments.

Pharmaceutical residues in sediments are concerning as ubiquitous emerging contaminants. Pyrite is the most abundant sulfide minerals in the estuarine and coastal sediments, making it a major sink for pharmaceutical pollutants such as sulfamethoxazole (SMX). However, research on the adsorption and redox behaviors of SMX on the pyrite surface is limited. Here, we investigated the impact of the nonphotochemical process of pyrite on the fate of coexisting SMX. Remarkably, sulfur vacancies (SVs) on pyrite promoted the generation of nonradical species (hydrogen peroxide, H2O2 and singlet oxygen, 1O2), thereby exhibiting prominent SMX degradation performance under darkness. Nonradical 1O2 contributed approximately 73.1% of the total SMX degradation. The SVs with high surrounding electron density showed an advanced affinity for adsorbing O2 and then initiated redox reactions in the sediment electron-storing geobattery pyrite, resulting in the extensive generation of H2O2 through a two-electron oxygen reduction pathway. Surface Fe(III) (hydro)oxides on pyrite facilitated the decomposition of H2O2 to 1O2 generation. Distinct nonradical products were observed in all investigated estuarine and coastal samples with the concentrations of H2O2 ranging from 1.96 to 2.94 µM, while the concentrations of 1O2 ranged from 4.63 × 10-15 to 8.93 × 10-15 M. This dark-redox pathway outperformed traditional photochemical routes for pollutant degradation, broadening the possibilities for nonradical species use in estuarine and coastal sediments. Our study highlighted the SV-triggered process as a ubiquitous yet previously overlooked source of nonradical species, which offered fresh insights into geochemical processes and the dynamics of pollutants in regions of frequent redox oscillations and sulfur-rich sediments.

[Distribution of Typical Resistant Bacteria and Resistance Genes in Source Water of the Middle and Lower Reaches of the Yellow River].

The Yellow River water of an urban area located in the middle and lower reaches of the Yellow River was taken as the research object， in which the seasonal and along-range distribution of total culturable bacteria， typical antibiotic resistant bacteria （amoxicillin resistant bacteria and sulfamethoxazole-resistant bacteria）， and their corresponding typical resistance genes ï¼»ß-lactam resistance gene （blaCTX-M） and sulfamamide resistance genes （sulI and sulⅡ）， as well as intⅠ1 were investigated. The results showed that the total culturable bacteria， ß-lactam-resistant bacteria and sulfonamide-resistant bacteria in the Yellow River Basin were significantly affected by temperature and human activities. The composition and quantity of their genera had obvious spatiotemporal distribution characteristics， in which Bacillus and Pseudomonas were dominant in the composition and number of bacteria. The abundance of resistance genes decreased with the decrease in temperature. The proportion of ß-lactam resistance genes in the total genes was higher than that of sulfanilamide genes， and sulI was the dominant gene in sulfanilamide genes. Correlation analysis showed that class Ⅰ integron played an important role in accelerating the spread of resistance genes. This study offers insight into the status quo of water resistance pollution in the Yellow River and provides theoretical support for the risk assessment of resistance genes in the middle and lower reaches of the Yellow River Basin.

[Adsorption Properties of Magnetic Phosphorous Camellia Oleifera Shells Biochar to Sulfamethoxazole in Water].

Magnetic phosphorous biochar （MPBC） was prepared from Camellia oleifera shells using phosphoric acid activation and iron co-deposition. The materials were characterized and analyzed through scanning electron microscopy （SEM）， X-ray diffractometry （XRD）， specific surface area and pore size analysis （BET）， Fourier infrared spectroscopy （FT-IR）， and X-ray photoelectron spectroscopy （XPS）. MPBC had a high surface area （1 139.28 m2·g-1） and abundant surface functional groups， and it could achieve fast solid-liquid separation under the action of an external magnetic field. The adsorption behavior and influencing factors of sulfamethoxazole （SMX） in water were investigated. The adsorbent showed excellent adsorption properties for SMX under acidic and neutral conditions， and alkaline conditions and the presence of CO32- had obvious inhibition on adsorption. The adsorption process conformed to the quasi-second-order kinetics and Langmuir model. The adsorption rate was fast， and the maximum adsorption capacity reached 356.49 mg·g-1. The adsorption process was a spontaneous exothermic reaction， and low temperature was beneficial to the adsorption. The adsorption mechanism was mainly the chemisorption of pyrophosphate surface functional groups （C-O-P bond） between the SMX molecule and MPBC and also included hydrogen bonding， π-π electron donor-acceptor （π-πEDA） interaction， and a pore filling effect. The development of MPBC adsorbent provides an effective way for resource utilization of waste Camellia oleifera shells and treatment of sulfamethoxazole wastewater.

Peroxymonosulfate activation by nanocomposites towards the removal of sulfamethoxazole: Performance and mechanism.

Heterogeneous activation of peroxomonosulfate (PMS) has been extensively studied for the degradation of antibiotics. The cobalt ferrite spinel exhibits good activity in the PMS activation, but suffers from the disadvantage of low PMS utilization efficiency. Herein, the nanocomposites including FeS, CoS2, CoFe2O4 and Fe2O3 were synthesized by hydrothermal method and used for the first time to activate PMS for the removal of sulfamethoxazole (SMX). The nanocomposites showed superior catalytic activity in which the SMX could be completely removed at 40 min, 0.1 g L-1 nanocomposites and 0.4 mM PMS with the first order kinetic constant of 0.2739 min-1. The PMS utilization efficiency was increased by 29.4% compared to CoFe2O4. Both radicals and non-radicals contributed to the SMX degradation in which high-valent metal oxo dominated. The mechanism analysis indicated that sulfur modification, on one hand, enhanced the adsorption of nanocomposites for PMS, and promoted the redox cycles of Fe2+/Fe3+ and Co2+/Co3+ on the other hand. This study provides new way to enhance the catalytic activity and PMS utilization efficiency of spinel cobalt ferrite.

Use of sawdust for production of ligninolytic enzymes by white-rot fungi and pharmaceutical removal.

Use of white-rot fungi for enzyme-based bioremediation of wastewater is of high interest. These fungi produce considerable amounts of extracellular ligninolytic enzymes during solid-state fermentation on lignocellulosic materials such as straw and sawdust. We used pure sawdust colonized by Pleurotus ostreatus, Trametes versicolor, and Ganoderma lucidum for extraction of ligninolytic enzymes in aqueous suspension. Crude enzyme suspensions of the three fungi, with laccase activity range 12-43 U/L and manganese peroxidase activity range 5-55 U/L, were evaluated for degradation of 11 selected pharmaceuticals spiked at environmentally relevant concentrations. Sulfamethoxazole was removed significantly in all treatments. The crude enzyme suspension from P. ostreatus achieved degradation of wider range of pharmaceuticals when the enzyme activity was increased. Brief homogenization of the colonized sawdust was also observed to be favorable, resulting in significant reductions after a short exposure of 5 min. The highest reduction was observed for sulfamethoxazole which was reduced by 84% compared to an autoclaved control without enzyme activity and for trimethoprim which was reduced by 60%. The compounds metoprolol, lidocaine, and venlafaxine were reduced by approximately 30% compared to the control. Overall, this study confirmed the potential of low-cost lignocellulosic material as a substrate for production of enzymes from white-rot fungi. However, monitoring over time in bioreactors revealed a rapid decrease in enzymatic ligninolytic activity.

The introduction of influent sulfamethoxazole loads induces changes in the removal pathways of sulfamethoxazole in vertical flow constructed wetlands featuring hematite substrate.

High frequent detection of sulfamethoxazole (SMX) in wastewater cannot be effectively removed by constructed wetlands (CWs) with a traditional river sand substrate. The role of emerging substrate of hematite in promoting SMX removal and the effect of influent SMX loads remain unclear. The removal efficiency of SMX in hematite CWs was significantly higher than that in river sand CWs by 12.7-13.8% by improving substrate adsorption capacity, plant uptake and microbial degradation. With increasing influent SMX load, the removal efficiency of SMX in hematite CWs slightly increased, and the removal pathways varied significantly. The contribution of plant uptake was relatively small (< 0.1%) under different influent SMX loads. Substrate adsorption (37.8%) primarily contributed to SMX removal in hematite CWs treated with low-influent SMX. Higher influent SMX loads decreased the contribution of substrate adsorption, and microbial degradation (67.0%) became the main removal pathway. Metagenomic analyses revealed that the rising influent load increased the abundance of SMX-degrading relative bacteria and the activity of key enzymes. Moreover, the abundance of high-risk ARGs and sulfonamide resistance genes in hematite CWs did not increase with the increasing influent load. This study elucidates the potential improvements in CWs with hematite introduction under different influent SMX loads.

Interaction patterns and keystone taxa of bacterial and eukaryotic communities during sulfamethoxazole mineralization in lake sediment.

Sulfamethoxazole (SMX) is a common antibiotic pollutant in aquatic environments, which is highly persistent under various conditions and significantly contributes to the spread of antibiotic resistance. Biodegradation is the major pathway to eliminate antibiotics in the natural environment. The roles of bacteria and eukaryotes in the biodegradation of antibiotics have received considerable attention; however, their successions and co-occurrence patterns during the biodegradation of antibiotics remain unexplored. In this study, 13C-labled SMX was amended to sediment samples from Zhushan Bay (ZS), West Shore (WS), and Gonghu Bay (GH) in Taihu Lake to explore the interplay of bacterial and eukaryotic communities during a 30-day incubation period. The cumulative SMX mineralization on day 30 ranged from 5.2 % to 19.3 %, which was the highest in WS and the lowest in GH. The bacterial community showed larger within-group interactions than between-group interactions, and the positive interactions decreased during incubation. However, the eukaryotic community displayed larger between-group interactions than within-group interactions, and the positive interactions increased during incubation. The proportion of negative interactions between bacteria and eukaryotes increased during incubation. Fifty genera (including 46 bacterial and 4 eukaryotic genera) were identified as the keystone taxa due to their dominance in the co-occurrence network and tolerance to SMX. The cumulative relative abundance of these keystone taxa significantly increased during incubation and was consistent with the SMX mineralization rate. These taxa closely cooperated and played vital roles in co-occurrence networks and microbial community interactions, signifying their crucial role in SMX mineralization. These findings broadened our understanding of the complex interactions of microorganisms under SMX exposure and their potential functions during SMX mineralization, providing valuable insights for in situ bioremediation.

Unlocking the power of activated carbon-mediated peracetic acid activation for efficient antibiotics abatement in groundwater: Coupling the processes of electron transfer, radical production, and adsorption.

The activation of peracetic acid (PAA) by activated carbon (AC) is a promising approach for reducing micropollutants in groundwater. However, to harness the PAA/AC system's potential and achieve sustainable and low-impact groundwater remediation, it is crucial to quantify the individual contributions of active species. In this study, we developed a combined degradation kinetic and adsorption mass transfer model to elucidate the roles of free radicals, electron transfer processes (ETP), and adsorption on the degradation of antibiotics by PAA in groundwater. Our findings reveal that ETP predominantly facilitated the activation of PAA by modified activated carbon (AC600), contributing to ∼61% of the overall degradation of sulfamethoxazole (SMX). The carbonyl group (CO) on the surface of AC600 was identified as a probable site for the ETP. Free radicals contributed to ∼39% of the degradation, while adsorption was negligible. Thermodynamic and activation energy analyses indicate that the degradation of SMX within the PAA/AC600 system requires a relatively low energy input (27.66 kJ/mol), which is within the lower range of various heterogeneous Fenton-like reactions, thus making it easily achievable. These novel insights enhance our understanding of the AC600-mediated PAA activation mechanism and lay the groundwork for developing efficient and sustainable technologies for mitigating groundwater pollution. ENVIRONMENTAL IMPLICATION: The antibiotics in groundwater raises alarming environmental concerns. As groundwater serves as a primary source of drinking water for nearly half the global population, the development of eco-friendly technologies for antibiotic-contaminated groundwater remediation becomes imperative. The innovative PAA/AC600 system demonstrates significant efficacy in degrading micropollutants, particularly sulfonamide antibiotics. By integrating degradation kinetics and adsorption mass transfer models, this study sheds light on the intricate mechanisms involved, emphasizing the potential of carbon materials as sustainable tools in the ongoing battle for clean and safe groundwater.

Adsorption effects of electron scavengers and inorganic ions on catalysts for catalytic oxidation of sulfamethoxazole in radiation treatment.

This study aimed to investigate adsorption effects of electron scavengers (H2O2 and S2O82-) on oxidation performance for mineralization of sulfamethoxazole (SMX) in radiation treatment using catalysts (Al2O3, TiO2). Hydrogen peroxide (H2O2, 1 mM) as an electron scavenger showed weak adsorption onto catalysts (0.012 mmol g-1-Al2O3 and 0.004 mmol g-1-TiO2, respectively), leading to an increase in TOC removal efficiency of SMX within the absorbed dose of 30 kGy by 12.3% with Al2O3 and by 8.0% with TiO2. The weak adsorption of H2O2 onto the catalyst allowed it to act as an electron scavenger, promoting indirect decomposition reactions. However, high adsorption of S2O82- (1 mM) onto Al2O3 (0.266 mmol g-1-Al2O3) showed a decrease in TOC removal efficiency of SMX from 76.2% to 30.2% within the absorbed dose of 30 kGy. The high adsorption of S2O82- onto the catalyst inhibited direct decomposition reaction by reducing adsorption of SMX on catalysts. TOC removal efficiency for Al2O3 without electron scavengers in an acidic condition was higher than that in a neutral or alkaline condition. However, TOC removal efficiency for Al2O3 with S2O82- was higher in a neutral condition than in other pH conditions. This indicates that the pH of a solution plays a critical role in the catalytic oxidation performance by determining surface charges of catalysts and yield of reactive radicals produced from water radiolysis. In the radiocatalytic system, H2O2 enhances the oxidation performance of catalysts (Al2O3 and TiO2) over a wide pH range (3-11). Meanwhile, S2O82- is not suitable with Al2O3 in acidic conditions because of its strong adsorption onto Al2O3 in this study.

New insights into bioaugmented removal of sulfamethoxazole in sediment microcosms: degradation efficiency, ecological risk and microbial mechanisms.

BACKGROUND: Bioaugmentation has the potential to enhance the ability of ecological technology to treat sulfonamide-containing wastewater, but the low viability of the exogenous degraders limits their practical application. Understanding the mechanism is important to enhance and optimize performance of the bioaugmentation, which requires a multifaceted analysis of the microbial communities. Here, DNA-stable isotope probing (DNA-SIP) and metagenomic analysis were conducted to decipher the bioaugmentation mechanisms in stabilization pond sediment microcosms inoculated with sulfamethoxazole (SMX)-degrading bacteria (Pseudomonas sp. M2 or Paenarthrobacter sp. R1). RESULTS: The bioaugmentation with both strains M2 and R1, especially strain R1, significantly improved the biodegradation rate of SMX, and its biodegradation capacity was sustainable within a certain cycle (subjected to three repeated SMX additions). The removal strategy using exogenous degrading bacteria also significantly abated the accumulation and transmission risk of antibiotic resistance genes (ARGs). Strain M2 inoculation significantly lowered bacterial diversity and altered the sediment bacterial community, while strain R1 inoculation had a slight effect on the bacterial community and was closely associated with indigenous microorganisms. Paenarthrobacter was identified as the primary SMX-assimilating bacteria in both bioaugmentation systems based on DNA-SIP analysis. Combining genomic information with pure culture evidence, strain R1 enhanced SMX removal by directly participating in SMX degradation, while strain M2 did it by both participating in SMX degradation and stimulating SMX-degrading activity of indigenous microorganisms (Paenarthrobacter) in the community. CONCLUSIONS: Our findings demonstrate that bioaugmentation using SMX-degrading bacteria was a feasible strategy for SMX clean-up in terms of the degradation efficiency of SMX, the risk of ARG transmission, as well as the impact on the bacterial community, and the advantage of bioaugmentation with Paenarthrobacter sp. R1 was also highlighted. Video Abstract.

Occurrence, distribution, and risk assessment of antibiotics in a typical aquaculture area around the Dongzhai Harbor mangrove forest on Hainan Island.

The trees of the Dongzhai Harbor mangrove forest suffer from antibiotic contamination from surrounding aquaculture areas. Despite this being one of the largest mangrove forests in China, few studies have focused on the antibiotic pollution status in these aquaculture areas. In the present study, the occurrence, distribution, and risk assessment of 37 antibiotics in surface water and sediment samples from aquaculture areas around Dongzhai Harbor mangrove forests were analyzed. The concentration of total antibiotics (∑antibiotics) ranged from 78.4 ng/L to 225.6 ng/L in surface water (except S14-A2) and from 19.5 ng/g dry weight (dw) to 229 ng/g dw in sediment. In the sediment, the concentrations of ∑antibiotics were relatively low (19.5-52.3 ng/g dw) at 75 % of the sampling sites, while they were high (95.7-229.0 ng/g dw) at a few sampling sites (S13-A1, S13D, S8D). The correlation analysis results showed that the Kd values of the 9 antibiotics were significantly positively correlated with molecular weight (MW), Kow, and LogKow. Risk assessment revealed that sulfamethoxazole (SMX) in surface water and SMX, enoxacin (ENX), ciprofloxacin (CFX), enrofloxacin (EFX), ofloxacin (OFX), and norfloxacin (NFX) in sediment had medium/high risk quotients (RQs) at 62.5 % and 25-100 %, respectively, of the sampling sites. The antibiotic mixture in surface water (0.06-3.36) and sediment (0.43-309) posed a high risk at 37.5 % and 66.7 %, respectively, of the sampling sites. SMX was selected as an indicator of antibiotic pollution in surface water to assist regulatory authorities in monitoring and managing antibiotic pollution in the aquaculture zone of Dongzhai Harbor. Overall, the results of the present study provide a comprehensive and detailed analysis of the characteristics of antibiotics in the aquaculture environment around the Dongzhai Harbor mangrove system and provide a theoretical basis for the source control of antibiotics in mangrove systems.

Development and validation of an UPLC-MS/MS assay for the simultaneous quantification of seven commonly used antibiotics in human plasma and its application in therapeutic drug monitoring.

OBJECTIVE: To develop and validate an UPLC-MS/MS assay for simultaneous determination of the total concentration of ceftazidime, ciprofloxacin, flucloxacillin, piperacillin, tazobactam, sulfamethoxazole, N-acetyl sulfamethoxazole and trimethoprim, and the protein-unbound concentration of flucloxacillin, in human plasma to be used for research and clinical practice. METHODS: Sample pretreatment included protein precipitation with methanol. For the measurement of protein-unbound flucloxacillin, ultrafiltration was performed at physiological temperature. For all compounds, a stable isotopically labelled internal standard was used. Reliability of the results was assessed by participation in an international quality control programme. RESULTS: The assay was successfully validated according to the EMA guidelines over a concentration range of 0.5-100 mg/L for ceftazidime, 0.05-10 mg/L for ciprofloxacin, 0.4-125 mg/L for flucloxacillin, 0.2-60 mg/L for piperacillin, 0.15-30 mg/L for tazobactam, 1-200 mg/L for sulfamethoxazole and N-acetyl sulfamethoxazole, 0.05-10 mg/L for trimethoprim and 0.10-50 mg/L for unbound flucloxacillin. For measurement of total concentrations, the within- and between-day accuracy ranged from 90.0% to 109%, and 93.4% to 108%, respectively. Within- and between-day precision (variation coefficients, CVs) ranged from 1.70% to 11.2%, and 0.290% to 5.30%, respectively. For unbound flucloxacillin, within-day accuracy ranged from 103% to 106% and between-day accuracy from 102% to 105%. The within- and between-day CVs ranged from 1.92% to 7.11%. Results of the international quality control programme showed that the assay is reliable. CONCLUSIONS: The method provided reliable, precise and accurate measurement of seven commonly prescribed antibiotics, including the unbound concentration of flucloxacillin. This method is now routinely applied in research and clinical practice.

Insights into the response of nitrogen metabolism to sulfamethoxazole contamination in constructed wetlands with varied substrates.

This study conducted an analysis of the variations in nitrogen metabolism pathways within constructed wetlands (CWs) using zeolite (CW-Z), ceramsite (CW-C), and lava (CW-L) under high concentration sulfamethoxazole (SMX) stress. The introduction of SMX hindered the formation of hydrogen bonds on the substrate surfaces; however, these surfaces still maintained a dense and thick biofilm. CW-Z exhibited superior removal efficiencies for ammonium nitrogen (NH4+-N) and nitrate nitrogen (NO3--N) compared to CW-C and CW-L, with removal rates of 92.54 ± 2.88 % and 89.39 ± 6.74 %, respectively. Interestingly, the proportion of genes involved in nitrification, denitrification and nitrate reduction genes in CW-C (36.05 %) were higher than that in CW-C (29.81 %) and CW-L (29.70 %) but the interactions among nitrogen functional bacteria in CW-Z were much more complex. Further analysis of the nitrogen metabolism pathway indicated that under CW-Z enhanced dissimilatory nitrate reduction SMX stress, while CW-L enhanced assimilatory nitrate reduction process compared to CW-C.

Ce/N @BC prepared based on plant metallurgy strategy: A novel activator of peroxymonosulfate for the degradation of sulfamethoxazole.

A novel carbon catalyst was created based on plant metallurgy strategy for organic pollutants removal. Plants rich in CeO2 NPs in water were used as carbon precursors and pyrolyzed with urea to obtain Ce/N co-doped carbon catalysts, which were used in the degradation of sulfamethoxazole (SMX) by active peroxymonosulfate (PMS). The results showed that the Ce/N @BC/PMS system achieved to 94.5% degradation of SMX in 40 min at a rate constant of 0.0602 cm-1. The activation center of PMS is widely dispersed Ce oxide nanocrystals, and CeO2 NPs promote the formation of oxygen centered PFR with enhanced catalytic ability and longer half-life. In addition, N-doping facilitates the transfer of π-electrons within the sp2 carbon of biochar, increasing active sites and thus improving PMS activation efficiency. The degradation process was contributed to by both radical and non-radical activation mechanisms including 1O2 and direct electron transfer, with O2•- serving as 1O2's precursor. Through the DFT calculations, LC-MS and toxicological analyses, the degradation pathway of pollutants and the toxicity changes throughout the entire degradation process were further revealed, indicating that the degradation of SMX could effectively reduce ecological toxicity.

Drought impact on pharmaceuticals in surface waters in Europe: Case study for the Rhine and Elbe basins.

Hydrological droughts are expected to increase in frequency and severity in many regions due to climate change. Over the last two decades, several droughts occurred in Europe, including the 2018-drought, which showed major adverse impacts for nature and different sectoral uses (e.g. irrigation, drinking water). While drought impacts on water quantity are well studied, little understanding exists on the impacts on water quality, particularly regarding pharmaceutical concentrations in surface waters. This study investigates the impact of the 2018-drought on concentrations of four selected pharmaceuticals (carbamazepine, sulfamethoxazole, diclofenac and metoprolol) in surface waters in Europe, with a major focus on the Elbe and Rhine rivers. Monitoring data were analysed for the period of 2010-2020 to estimate the spatiotemporal patterns of pharmaceuticals and assess the concentration responses in rivers during the 2018-drought compared to reference years. Our results indicate an overall deterioration in water quality, which can be attributed to the extremely low flow and higher water temperatures (∼ + 1.5 °C and + 2.0 °C in Elbe and Rhine, respectively) during the 2018-drought. Our results show an increase in the concentrations of carbamazepine, sulfamethoxazole, and metoprolol, but reduced concentrations of diclofenac during the 2018-drought. Significant increases in carbamazepine concentrations (+45 %) were observed at 3/6 monitoring stations in the upstream part of the Elbe, which was mainly attributed to less dilution of chemical loads from wastewater treatment plants under drought conditions. However, reduced diclofenac concentrations could be attributed to increased degradation processes under higher water temperatures (R2 = 0.60). Moreover, the rainfed-dominated Elbe exhibited more severe water quality deterioration than the snowmelt-dominated Rhine river, as the Elbe's reduction in dilution capacity was larger. Our findings highlight the need to account for the impacts of climate change and associated increases in droughts in water quality management plans, to improve the provision of water of good quality for ecosystems and sectoral needs.

Enzyme-induced reactive oxygen species trigger oxidative degradation of sulfamethoxazole within a methanotrophic biofilm.

Although microorganisms carrying copper-containing membrane-bound monooxygenase (CuMMOs), such as particulate methane monooxygenase (pMMO) and ammonia monooxygenase (AMO), have been extensively documented for their capability to degrade organic micropollutants (OMPs), the underlying reactive mechanism remains elusive. In this study, we for the first time demonstrate biogenic reactive oxygen species (ROS) play important roles in the degradation of sulfamethoxazole (SMX), a representative OMP, within a methane-fed biofilm. Highly-efficient and consistent SMX biodegradation was achieved in a CH4-based membrane biofilm reactor (MBfR), manifesting a remarkable SMX removal rate of 1210.6 ± 39.0 µg·L-1·d-1. Enzyme inhibition and ROS clearance experiments confirmed the significant contribution of ROS, which were generated through the catalytic reaction of pMMO and AMO enzymes, in facilitating SMX degradation. Through a combination of density functional theory (DFT) calculations, electron paramagnetic resonance (EPR) analysis, and transformation product detection, we elucidated that the ROS primarily targeted the aniline group in the SMX molecule, inducing the formation of aromatic radicals and its progressive mineralization. In contrast, the isoxazole-ring was not susceptible to electrophilic ROS attacks, leading to accumulation of 3-amino-5-methylisoxazole (3A5MI). Furthermore, microbiological analysis suggested Methylosarcina (a methanotroph) and Candidatus Nitrosotenuis (an ammonia-oxidizing archaea) collaborated as the SMX degraders, who carried highly conserved and expressed CuMMOs (pMMO and AMO) for ROS generation, thereby triggering the oxidative degradation of SMX. This study deciphers SMX biodegradation through a fresh perspective of free radical chemistry, and concurrently providing a theoretical framework for the advancement of environmental biotechnologies aimed at OMP removal.

Sulfamethoxazole stress endangers the gut health of sea cucumber (Apostichopus japonicus) and affects host metabolism.

Sulfamethoxazole (SMZ) is a frequently detected antibiotic in the environment, and there is a growing concern about its potential toxic effects on aquatic organisms. sea cucumber (Apostichopus japonicas) is a benthic invertebrate whose gut acts as a primary immune defense and serves critical protective barrier. In this study, growth performance, histology, gut microbiota, and metabolomics analyses were performed to investigate the toxic response in the intestine of sea cucumber effects caused by SMZ stress for 56 d by evaluating with different concentrations of SMZ (0, 1.2×10-3, and 1.2 mg/L). The weight gain rate of sea cucumbers under SMZ stress showed significant decrease, indicating that the growth of sea cucumbers was hindered. Analysis of the intestinal morphological features indicated that SMZ stimulation resulted in atrophy of the sea cucumber gut. In the 1.2×10-3 mg/L concentration, the thickness of muscle and mucosal layers was reduced by 12.40% and 21.39%, while in the 1.2 mg/L concentration, the reductions were 35.08% and 26.98%. The abundance and diversity of sea cucumber intestinal bacteria decreased significantly (P < 0.05) under the influence of SMZ. Notably, the intestinal bacteria of sea cucumber became homogenized with the increase in SMZ concentration, and the relative abundance of Ralstonia reached 81.64% under the stress of 1.2 mg/L concentration. The SMZ stress significantly impacted host metabolism and disrupted balance, particularly in L-threonine, L-tyrosine, neuronic acid, piperine, and docosapentaenoic acid. SMZ leads to dysregulation of metabolites, resulting in growth inhibition and potential inflammatory responses that could adversely affect the normal activities of aquatic organisms. Further metabolic pathway enrichment analyses demonstrated that impaired biosynthesis of unsaturated fatty acids and aminoacyl-tRNA biosynthesis metabolic pathway were major reasons for SMZ stress-induced intestinal bacteria dysbiosis. This research aims to provide some theoretical evidence for the ecological hazard assessment of antibiotics in water.