[Occurrence Characteristics and Ecological Risk Assessment of Antibiotics in Reclaimed Water-receiving Rivers in Beijing].

Taking Liangshui River, the reclaimed water-receiving river in Beijing, as the research area, the types, detection frequencies, and concentrations of 16 antibiotics in water and sediment were analyzed, and their temporal-spatial variation and occurrence characteristics were discussed. The results showed that nine and 13 target antibiotics were detected in the water and sediment of Liangshui River, with the antibiotic concentration ranges of ND-116.68 ng·L-1 and ND-235.42 ng·g-1, respectively. The main antibiotics in water were ofloxacin and clarithromycin, and the main antibiotic in sediment was ofloxacin. The total concentration of antibiotics in water and sediment showed a gradual decrease from the upstream to the downstream in the Liangshui River mainstream, and the concentration of antibiotics in tributaries was higher than that in the mainstream. The inflow of tributaries had an obvious impact on the antibiotic concentration in water for the Liangshui River but had little impact on its sediment. The total concentration of antibiotics in water and sediment during the dry season was generally higher than that during the wet season. The detected antibiotics with the highest concentration were quinolones in water during the wet season and macrolides in the dry season. Quinolones had the highest concentration in sediment in both seasons. The ecological risk assessment results showed that clarithromycin had a low risk in water in the dry season and sediment in both seasons, whereas the other antibiotics had no risk. The combined ecological risk and the most sensitive trophic level ecological risk assessment showed that all sampling sites had low risk or no risk, and the risk of the dry season was generally greater than that of the wet season. The risk values of some sampling points were close to the medium risk threshold during the dry season, which requires further attention.

The construction of ofloxacin detection in fish matrix based on a shark-derived single-domain antibody.

BACKGROUND: Due to the serious issue of ofloxacin (OFL) abuse, there is an increasingly urgent need for accurate and rapid detection of OFL. Immunoassay has become the "golden method" for detecting OFL in complex matrix beneficial to its applicability for a large-scale screening, rapidity, and simplicity. However, traditional antibodies used in immunoassay present challenges such as time-consuming preparation, unstable sensitivity and specificity, and difficulty in directional evolution. In this paper, we successfully developed an OFL detection method based on a shark-derived single-domain antibody (ssdAb) to address these issues. RESULTS: Using phage display technology and a heterologous expression system, OFL-specific clones 1O11, 1O13, 1O17, 1O19, 1O21, and 2O26 were successfully isolated and expressed in soluble form. Among all OFL-specific ssdAbs, the 1O17 ssdAb exhibited the highest binding affinity to OFL in a concentration-dependence manner. The limit of detection (IC10) of 1O17 ssdAb was calculated as 0.34 ng/mL with a detection range of 3.40-1315.00 ng/mL, and its cross reactivity with other analogs was calculated to be less than 5.98 %, indicating high specificity and sensitivity. Molecular docking results revealed that 100Trp and 101Arg located in the CDR3 region of 1O17 ssdAb were crucial for OFL binding. In fish matrix performance tests, the 1O17 ssdAb did not demonstrate severe matrix interference in OFL-negative fish matrix, achieving satisfactory recovery rates ranging from 83.04 % to 108.82 % with high reproducibility. SIGNIFICANCE: This research provides a new and efficient OFL detection recognition element with significant potential in immunoassay applications, broadening the application scenarios of ssdAbs. It offers valuable insights into the structure-activity relationship between ssdAbs and small molecules, laying a theoretical foundation for the further directional modification and maturation of ssdAbs in subsequent applications.

A novel ratiometric electrochemical sensing platform combined with molecularly imprinted polymer and Fe-MOF-NH2/CNTs-NH2/MXene composite for efficient detection of ofloxacin.

BACKGROUND: Ofloxacin (OFL) is often abused in medicine and animal husbandry, which poses a great threat to human health and ecological environment. Therefore, it is necessary to establish efficient method to detect OFL. Electrochemical sensor has attracted widespread attention due to the advantages of low cost and fast response. However, most electrochemical sensors usually use one response signal to detect the target, which makes it sensitive to the variable background noise in the complex environment, resulting in low robustness and selectivity. The ratio detection mode and employing molecularly imprinted polymer (MIP) are two strategies to solve these problems. RESULTS: A novel molecular imprinting polymer-ratiometric electrochemical sensor (MIP-RECS) based on Fe-MOF-NH2/CNTs-NH2/MXene composite was prepared for the rapid and sensitive detection of OFL. The positively charged Fe-MOF-NH2 and CNTs-NH2 as interlayer spacers were introduced into the negatively charged MXene through a simple electrostatic self-assembly technique, which effectively prevented the agglomeration of MXene and increased the electrocatalytic activity. A glass carbon electrode was modified by the composite and a MIP film was electropolymerized on it using o-phenylenediamine and ß-cyclodextrin as bifunctional monomers and OFL as template. Then a MIP-RECS was designed by adding dopamine (DA) into the electrolyte solution as internal reference, and OFL was quantified by the response current ratio of OFL to DA. The current ratio and the concentration of OFL displayed a satisfying linear relationship in the range of 0.1 µM-100 µM, with a limit of detection (LOD) of 13.2 nM. SIGNIFICANCE: Combining molecular imprinting strategy and ratio strategy, the MIP-RECS has impressive selectivity compared with the non-imprinted polymer-RECS, and has better repeatability and reproducibility than non-ratiometric sensor. The MIP-RECS has high sensitivity and accuracy, which was applied for the detection of OFL in four different brands of milk and was verified by HPLC method with satisfactory results.

Combining GC-MS/MS with a LLE-SPE sample pretreatment step to simultaneously analyse enrofloxacin and ofloxacin residues in chicken tissues and pork.

A widely applicable original gas chromatography-tandem mass spectrometry (GC-MS/MS) method was explored to qualitatively and quantitatively measure enrofloxacin and ofloxacin residues in chicken tissues and pork. The experimental samples were processed based on liquid-liquid extraction (LLE) and solid-phase extraction (SPE). Trimethylsilyl diazomethane (TMSD) was chosen to react derivatively with enrofloxacin and ofloxacin. In total, 78.25% âˆ¼ 90.56% enrofloxacin and 78.43% âˆ¼ 91.86% ofloxacin was recovered from the blank fortified samples. The limits of detection (LODs) were 0.7-1.0 µg/kg and 0.1-0.2 µg/kg, respectively. The limits of quantitation (LOQs) were 1.6-1.9 µg/kg and 0.3-0.4 µg/kg, respectively. It was verified that various experimental data met the requirements of the FAO & WHO (2014) for the detection of veterinary drug residues. Real samples obtained from local markets were analysed using the established method, and no residues of enrofloxacin or ofloxacin were detected in the samples.

Synthesis of highly luminescent core-shell nanoprobes in a single pot for ofloxacin detection in blood serum and water.

Antibiotics are commonly used as antibacterial medications due to their extensive and potent therapeutic properties. However, the overconsumption of these chemicals leads to their accumulation in the human body via the food chain, amplifying drug resistance and compromising immunity, thus presenting a significant hazard to human health. Antibiotics are classified as organic pollutants. Therefore, it is crucial to conduct research on precise methodologies for detecting antibiotics in many substances, including food, pharmaceutical waste, and biological samples like serum and urine. The methodology described in this research paper introduces an innovative technique for producing nanoparticles using silica as the shell material, iron oxide as the core material, and carbon as the shell dopant. By integrating a carbon-doped silica shell, this substance acquires exceptional fluorescence characteristics and a substantial quantum yield value of 80%. By capitalising on this characteristic of the substance, we have effectively constructed a fluorescent sensor that enables accurate ofloxacin analysis, with a detection limit of 1.3 × 10-6 M and a linear range of concentrations from 0 to 120 × 10-6 M. We also evaluated the potential of CSIONPs for OLF detection in blood serum and tap water analysis. The obtained relative standard deviation values were below 3.5%. The percentage of ofloxacin recovery from blood serum ranged from 95.52% to 103.28%, and from 89.9% to 96.0% from tap water.

Simultaneous identification and enantioseparation of ofloxacin and duloxetine without the single standard and computational calculation of their inclusion complexes.

Given the markedly different pharmacological activities between enantiomeric isomers, it is crucial to encourage the stereoselective determination of chiral drugs in the biological and pharmaceutical fields, and the combination of drugs makes this analysis more complicated and challenging. Herein, a capillary electrophoresis (CE) method for the enantioseparation of ofloxacin and duloxetine was established, enabling the simultaneous identification of four isomers in nonracemic mixtures with enantiomeric excess (ee%) values exceeding 5%. This was achieved through the integration of theoretical simulation and electron circular dichroism (ECD), all without reliance on individual standards. Molecular modeling explained and verified the migration time differences of these isomers in electrophoretic separation. Moreover, the correlation coefficients (R2 ) between the enantiomeric peak area differentials and ee% were both above 0.99. Recovery rates were quantified using bovine serum as the matrix, with results ranging from 93.32% to 101.03% (RSD = 0.030) and 92.69% to 100.52% (RSD = 0.028) for these two chiral drugs at an ee value of 23.1%, respectively.

[Characteristics and Risk Assessment of Antibiotic Contamination in Oujiang River Basin in Southern Zhejiang Province].

Antibiotic pollution in the environment has a negative impact on ecosystem security. Taking the Oujiang River Basin as an example,high-performance liquid chromatography mass spectrometry(LC-MS)was used to detect the concentration of six classes of 35 antibiotics in the surface water of the southern Zhejiang River Basin. The concentration level and spatial distribution of antibiotics were analyzed,the risk of antibiotics to ecology and human health were assessed using relevant models,and the sources of antibiotics were discussed. The results showed that in 20 sampling sites,a total of four classes of 12 antibiotics were detected,including sulfonamides,quinolones,tetracyclines,and lincosamides. The total concentration was ND-1 018 ng·L-1. The highest detection rate was that of Lincomycin(90.48%),followed by that of sulfapyridine(38.10%). The three antibiotics with the highest average concentrations were ofloxacin(12.49 ng·L-1),Lincomycin(11.08 ng·L-1),and difloxacin(7.38 ng·L-1). Antibiotics in the basin showed mainly spotty pollution,which had large spatial differentiation. The average concentration of antibiotics in the upstream(54.39 ng·L-1)was higher than that mid-downstream(46.64 ng·L-1). The degree of antibiotic pollution from upstream to downstream showed a characteristic of being "sparse in the upstream and dense in the downstream. " This indicated that the concentration of antibiotics in the upstream was significantly different,whereas the pollution degree of antibiotics in the downstream was uniform. The upstream was mainly polluted by health,livestock,and poultry breeding wastewater emissions,and downstream pollution was mainly caused by densely populated activities and the rapid development of economy,trade,and industry. The ecological risk assessment results showed that the upstream site H6 had the highest risk quotient,ofloxacin and enrofloxacin had high risk levels, and lincomycin had a moderate risk level. Health risk assessment results showed that the Oujiang River surface water antibiotics posed no risk to human health.

Dissociation Kinetics and Antimicrobial Activity of Ofloxacin Antibiotic in Artificial Tears Via 1H-NMR, Raman, and UV-Vis Spectroscopic Analysis.

Introduction: The hydrogen-bonded networks play a significant role in influencing several physicochemical properties of ofloxacin in artificial tears (ATs), including density, pH, viscosity, and self-diffusion coefficients. The activities of the ofloxacin antibiotic with Ats mixtures are not solely determined by their concentration but are also influenced by the strength of the hydrogen bonding network which highlight the importance of considering factors such as excessive tear production and dry eye conditions when formulating appropriate dosages of ofloxacin antibiotics for eye drops. Objectives: Investigating the physicochemical properties of ofloxacin-ATs mixtures, which serve as a model for understanding the impact of hydrogen bonding on the antimicrobial activity of ofloxacin antibiotic eye drops. Determine the antimicrobial activities of the ofloxacin-Ats mixture with different concentration of ofloxacin. Methods: The ofloxacin-ATs mixtures were analyzed using 1H-NMR, Raman, and UV-Vis spectroscopies, with variation of ofloxacin concentration to study its dissociation kinetics in ATs, mimicking its behavior in human eye tears. The investigation includes comprehensive analysis of 1H-NMR spectral data, self-diffusion coefficients, Raman spectroscopy, UV-Vis spectroscopy, liquid viscosity, and acidity, providing a comprehensive assessment of the physicochemical properties. Results: Analysis of NMR chemical shifts, linewidths, and self-diffusion coefficient curves reveals distinct patterns, with peaks or minima observed around 0.6 ofloxacin mole fraction dissociated in ATs, indicating a strong correlation with the hydrogen bonding network. Additionally, the pH data exhibits a similar trend to viscosity, suggesting an influence of the hydrogen bonding network on protonic ion concentrations. Antibacterial activity of the ofloxacin-ATs mixtures is evaluated through growth rate analysis against Salmonella typhimurium, considering varying concentrations with mole fractions of 0.1, 0.4, 0.6, 0.8, and 0.9. Conclusions: The antibiotic-ATs mixture with a mole fraction of 0.6 ofloxacin exhibited lower activity compared to mixtures with mole fractions of 0.1 and 0.4, despite its lower concentration. The activities of the mixtures are not solely dependent on concentration but are also influenced by the strength of the hydrogen bonding network. These findings emphasize the importance of considering tear over-secretion and dry eye problems when designing appropriate doses of ofloxacin antibiotics for eye drop formulations.

Ln-MOF-Based Hydrogel Films with Tunable Luminescence and Afterglow Behavior for Visual Detection of Ofloxacin and Anti-Counterfeiting Applications.

Highly selective and sensitive quantitative detection of ofloxacin (OFX) at ultralow concentrations in aqueous media and development of new afterglow materials remains a challenge. Herein, a new 2D water-stable lanthanide metal-organic framework (NIIC-2-Tb) is proposed, which exhibits high selectivity towards OFX through the luminescence quenching with the lowest detection limit (1.1 × 10-9 M) reported to date and a fast response within 6 s. In addition, the luminescent detection of OFX by NIIC-2-Tb is not affected by typical components of blood plasma and urine. The excellent sensing effect of NIIC-2-Tb is further utilized to prepare a composite functional sensing carrageenan hydrogel material for the rapid detection of OFX in meat in real time and the first discovery of impressive afterglow in MOF-based hydrogels. This study not only presents novel Ln-MOF materials and Ln-MOF-based hydrogel films for luminescent sensing of OFX, but also demonstrates color-tunable luminescent films with afterglow, which expands the application of composite luminescent materials for detection and anti-counterfeiting.

Comparative analysis of SilA-laccase mediated degradation of ciprofloxacin, norfloxacin and ofloxacin and interpretation of the possible catalytic mechanism.

Fluoroquinolones (FQs) are the most commonly used antimicrobial drugs and regardless of their advantages in the healthcare sector, the pollution of these antimicrobial drugs in the environment has big concerns about human and environmental health. The presence of these antibiotic drugs even at the lowest concentrations in the environment has resulted in the emergence and spread of antibiotic resistance. Hence, it is necessary to remediate these pollutants from the environment. Previously alkaline laccase (SilA) from Streptomyces ipomoeae has been demonstrated to show degrading potentials against two of the FQs, Ciprofloxacin (CIP) and Norfloxacin (NOR); however, the molecular mechanism was not elucidated in detail. In this study, we have analyzed the possible molecular catalytic mechanism of FQ degrading SilA-laccase for the degradation of the FQs, CIP, NOR and Ofloxacin (OFL) using three-dimensional protein structure modeling, molecular docking and molecular dynamic (MD) studies. The comparative protein sequence analysis revealed the presence of tetrapeptide conserved catalytic motif, His102-X-His104-Gly105. After evaluating the active site of the enzyme in depth using CDD, COACH and S-site tools, we have identified the catalytic triad composed of three conserved amino acid residues, His102, Val103 and Tyr108 with which ligands interacted during the catalysis process. By analyzing the MD trajectories, it is revealed that the highest degradation potential of SilA is for CIP followed by NOR and OFL. Ultimately, this study provides the possible comparative catalytic mechanism for the degradation of CIP, NOR and OFL by the SilA enzyme.Communicated by Ramaswamy H. Sarma.

Occurrence, removal, emission and environment risk of 32 antibiotics and metabolites in wastewater treatment plants in Wuhu, China.

Wastewater treatment plants (WWTPs) are considered important sources of antibiotics and metabolites in aquatic environments and pose a serious threat to the safety of aquatic organisms. In this study, we investigated the seasonal occurrence, removal, emission, and environmental risk assessment (ERA) of 32 antibiotics and metabolites at four WWTPs located in Wuhu, China. The main findings of this study are as follows: Ofloxacin concentrations dominated all WWTPs, and large quantities of sulfachinoxalin were only detected in WWTP 2 treating mixed sewage. The average apparent removal of individual parent antibiotics or metabolites ranged from -94.7 to 100 %. There was a noticeable seasonal emission pattern (independent t-test, t = 9.89, p < 0.001), with lower emissions observed during summer. WWTPs discharged 85.2 ± 43.8 g of antibiotics and metabolites each day. Approximately 87 % of emissions were discharged into the mainstream of the Yangtze River, while the remainder were discharged into its tributary, the Zhanghe River. The total emissions of 21 parent antibiotics were approximately 18 % of the prescription data, indicating that a considerable and alarming amount of prototype drugs entered the receiving water body. Based on the risk quotient (RQ) of the ERA, the Zhanghe River has a moderate risk of ofloxacin (RQ = 0.111-0.583), a low or insignificant risk of sulfamethoxazole (RQ = 0.003-0.048), and an insignificant risk of other antibiotics or metabolites. However, the risk of antibiotics or metabolites in the mainstream of Yangtze River is insignificant. This study could help understand the seasonal emission patterns of antibiotics and metabolites, as well as more antibiotics sensitive of environmental risks in tributary than that in mainstream.

Groundwater antibiotics contamination in an alluvial-pluvial fan, North China Plain: Occurrence, sources, and risk assessment.

Antibiotics in groundwater have received widespread concern because high levels of them harm aquatic ecosystems and human health. This study aims to investigate the concentration, distribution, ecological and human health risks as well as potential sources of antibiotics in groundwater in the Hutuo River alluvial-pluvial fan, North China Plain. A total of 84 groundwater samples and nine surface water samples were collected, and 35 antibiotics were analyzed using ultra-performance liquid chromatography-tandem mass spectrometry. The results indicated that 12 antibiotics were detected in surface water with the total concentrations ranging from 5.33 ng/L to 64.73 ng/L. Macrolides were the primary category of antibiotics with a detection frequency of 77.8% (mean concentration: 9.14 ng/L). By contrast, in shallow granular aquifers (<150 m), 23 antibiotics were detected and the total concentrations of them ranged from below the method detection limit to 465.26 ng/L (detection frequency: 39.7%). Quinolones were the largest contributor of antibiotics with detection frequency and mean concentration of 32.1% and 12.66 ng/L, respectively. And ciprofloxacin and ofloxacin were the two preponderant individual antibiotics. The mean concentration of groundwater antibiotics in peri-urban areas was approximately 1.7-4.9 times that in other land use types. Livestock manure was the predominant source of antibiotics in groundwater. Erythromycin, sulfametoxydiazine, ofloxacin, and cinoxacin exhibited medium ecological risks to aquatic organisms. All antibiotics posed no risks to human health. The findings of this study provide valuable insights into the occurrence and management of antibiotic contamination in the groundwater in the Hutuo River alluvial-pluvial fan.

Validated spectrofluorimetric assay of two co-administered drug mixtures containing hydroxychloroquine with either moxifloxacin or ofloxacin as a drug regimen for hospital-acquired pneumonia in patients with COVID-19.

Moxifloxacin and ofloxacin are two broad-spectrum quinolone antibiotics. They are among the most widely used antibiotics, at this time, applied to control the COVID-19 pandemic. Hydroxychloroquine is an FDA-approved drug for the treatment of COVID-19. This work describes a simple, green, selective, and sensitive spectrofluorimetric method for the assay of moxifloxacin and ofloxacin in the presence of hydroxychloroquine, two co-administered mixtures used in the treatment of hospital-acquired pneumonia in patients with COVID-19. Simultaneous assay of hydroxychloroquine and moxifloxacin was carried out in methanol using a direct spectrofluorimetric method (method I) at 375 and 550 nm, respectively, after excitation at 300 nm. The direct spectrofluorimetric assay was rectilinear over concentration ranges 50.0-400.0 and 300.0-2500.0 ng/ml for hydroxychloroquine and moxifloxacin, respectively, with limits of detection (LOD) of 6.4 and 33.64 ng/ml and limits of quantitation (LOQ) of 19.4 and 102.6 ng/ml, respectively, for the two drugs. The assay for hydroxychloroquine and ofloxacin was carried out by measuring the first derivative synchronous amplitude for hydroxychloroquine at the zero crossing point of ofloxacin and vice versa at Δλ = 140 nm (method II). Hydroxychloroquine was measured at 266 nm, while ofloxacin was measured at 340 nm over the concentration range 4-40 ng/ml for hydroxychloroquine and 200-2000 ng/ml for ofloxacin with LOD of 0.467 and 25.3 ng/ml and LOQ of 1.42 and 76.6 ng/ml, respectively, for the two drugs. The two methods were validated following International Conference on Harmonization guidelines and were applied to the analysis of the two drugs in plasma with good percentage recoveries (109.73-93.17%).

Adsorption kinetics of ciprofloxacin and ofloxacin by green-modified carbon nanotubes.

This paper investigated the uptake of CIP and OFL in single and multicomponent adsorptive systems using modified carbon nanotubes (CNTs) as adsorbent material. The characterization analyses of the pre- and post-process material by XPS, TG/DTG, FT-IR, SEM/EDS, and XRD helped in the elucidation of the mechanisms, indicating greater involvement of n-n and π -π interactions. In the kinetic studies, the simple systems with CIP and OFL were similar, both showed equilibrium time around 20/30 min and increased adsorptive capacity with increasing initial drug concentration. In the multicomponent system, different fractions of CIP and OFL were tested and the time to reach equilibrium also varied between 20 and 30 min. In general, the adsorption capacity of CIP is slightly lower than that of OFL under the conditions tested. The selectivity analysis of the system showed that the selectivity's of the two drugs are identical in equimolar fractions. The mathematical modeling of the kinetic data indicated that in monocomponent systems, the model of pseudo-second order (PSO) adequately described both CIP and OFL kinetics. Furthermore, with the implementation of Artificial Neural Networks (ANN), it was possible to obtain a more assertive prediction of the behavior of single and binary systems.

Pharmaceutical active compounds in a heavily industrialized and urbanized bay, Eastern China.

Bays are transition zones connecting freshwater ecosystems and marine ecosystems, and they are strongly influenced by intensive human activities. Pharmaceuticals are of concern in bay aquatic environments because of their potential threat to marine food web. We studied the occurrence, spatial distribution, and ecological risks of 34 pharmaceutical active compounds (PhACs) in Xiangshan Bay, a heavily industrialized and urbanized area in Zhejiang Province, Eastern China. PhACs were ubiquitously detected in the coastal waters of the study area. A total of twenty-nine compounds were detected in at least one sample. Carbamazepine, lincomycin, diltiazem, propranolol, venlafaxine, anhydro erythromycin, and ofloxacin had the highest detection rate (≥ 93%). These compounds were detected with maximum concentrations of 31, 127, 0.52, 1.96, 2.98, 75, and 98 ng/L, respectively. Human pollution activities included marine aquacultural discharge and effluents from the local sewage treatment plants. These activities were the most influential sources in this study area based on principal component analysis. Lincomycin was an indicator of veterinary pollution of coastal aquatic environment, and the concentrations of lincomycin were positively related to the total phosphorus in this area (r = 0.28, p < 0.05). Typical PhACs such as venlafaxine, ofloxacin, norfloxacin, roxithromycin, and clarithromycin were significantly and positively correlated with nitrate and total nitrogen (r > 0.26, p < 0.05) based on Pearson's correlation analysis. Carbamazepine was negatively correlated with salinity (r < - 0.30, p < 0.01). Land use pattern was also correlated with the occurrence and distribution of PhACs in the Xiangshan Bay. Some PhACs, i.e., ofloxacin, ciprofloxacin, carbamazepine, and amitriptyline posed medium to high ecological risks to this coastal environment. The results of this study could be helpful to understand the levels of pharmaceuticals, potential sources, and ecological risks in marine aquacultural environment.

Use of Fluorescence Spectroscopy and Chemometrics to Visualise Fluoroquinolones Photodegradation Major Trends: A Confirmation Study with Mass Spectrometry.

In this work, we employed EEM-PARAFAC (fluorescence excitation-emission matrices-parallel factor analysis) as a low-cost tool to study the oxidation pathways of (fluoro)quinolones. Amounts of 12.5 µM of enrofloxacin (ENR), ciprofloxacin (CIP), ofloxacin (OFL), oxolinic acid (OA), and flumequine (FLU), as individual solutions, were irradiated under UVA light. A 5-component PARAFAC model was obtained, four of them related to the parent pollutants, named as ENR-like (including CIP), OFL-like, OA-like, and FLU-like, and an additional one related to photoproducts, called ENRox-like (with an emission red-shift with respect to the ENR-like component). Mass spectrometry was employed to correlate the five PARAFAC components with their plausible molecular structures. Results indicated that photoproducts presenting: (i) hydroxylation or alkyl cleavages exhibited fingerprints analogous to those of the parent pollutants; (ii) defluorination and hydroxylation emitted within the ENRox-like region; (iii) the aforementioned changes plus piperazine ring cleavage emitted within the OA-like region. Afterwards, the five antibiotics were mixed in a single solution (each at a concentration of 0.25 µM) in seawater, PARAFAC being also able to deconvolute the fingerprint of humic-like substances. This approach could be a potential game changer in the analysis of (fluorescent) contaminants of emerging concern removals in complex matrices, giving rapid visual insights into the degradation pathways.

Mechanism of downward migration of quinolone antibiotics in antibiotics polluted natural soil replenishment water and its effect on soil microorganisms.

Reclaimed water is widely concerned as an effective recharge of groundwater and surface water, but trace organic pollutants produced by traditional wastewater treatment plants (WWTPs) would cause environmental pollution (water and soil) during infiltration. Therefore, the effects of reclaimed water containing ofloxacin (OFL) and ciprofloxacin (CIP) in antibiotics polluted natural soil (APNS) were investigated by simulating soil aquifer treatment systems (SATs). The experiment results showed that OFL and CIP in water were adsorbed and microbially degraded mainly at 30 cm, and the concentration of OFL and CIP in soil increased with depth, which were mainly due to the desorption from APNS. Concurrently, the change in replenishment water concentration also significantly affected OFL and CIP in pore water and soil. Although OFL and CIP inhibited the diversity of soil microbial community, they also promoted the growth of some microorganisms. As the dominant bacteria, Proteobacteria and Acidobacteriota can effectively participate in the degradation of OFL and CIP. The degradation effects of soil microorganisms on OFL and CIP were 45.48% and 42.39%, respectively, indicating that soil microorganisms selectively degraded pollutants. This experiment was carried out on APNS, which provided a reference for future studies on the migration of trace organic pollutants under natural conditions.

Determination of quinolone antibiotics in honey by pH-induced natural deep eutectic solvent combined with vortex-assisted dispersive liquid-liquid microextraction.

A green, fast, and efficient pH-induced natural deep eutectic solvent combined with vortex-assisted dispersive liquid-liquid microextraction method (pH-NADES-VA-DLLME) followed by HPLC was established for determination of ofloxacin (OFL), ciprofloxacin (CIP) and enrofloxacin (ENR) in honey. In this method, NaOH, as an emulsifier, can increase the contact area between the NADES and the sample solution, which can efficiently improve the extraction efficiency of the analytes. Moreover, HCl acts as the phase separation agent without centrifugation in the process, which can greatly enhance the efficiency of the sample analysis process. In addition, the main factors affecting the extraction effect were optimized by single factor experiments. Under the optimal conditions, the limits of detection (LODs), the limits of quantification (LOQs) and recoveries were in the range of 0.004-0.015 µg mL-1, 0.012-0.050 µg mL-1, and 98.0-112.5%, respectively. The RSD values of intra-day and inter-day precisions were no more than 5.5% and 6.0%, respectively. The developed method was successfully applied to determine the three quinolone antibiotics in honey.

A high-precision prediction for spatiotemporal distribution and risk assessment of antibiotics in an urban watershed using a hydrodynamic model.

A methodology for the high-precision prediction and risk assessment of antibiotics at the watershed scale was established. Antibiotic emission inventory and attenuation processes were integrated into the MIKE 11 model to predict the spatiotemporal distribution of norfloxacin, ofloxacin, enrofloxacin, erythromycin, roxithromycin, and sulfamethoxazole in the Nanfei River watershed, China. Considering the variations in antibiotic removal in sewage treatment plants, manure composting, and lagoon systems, the high, medium, and low removal efficiencies of selected antibiotics across China were obtained and used as the best, expected, and worst scenarios, respectively, to evaluate the uncertainty of antibiotic emissions. The predicted concentrations were comparable to antibiotic measurements after flow calibration. The prediction results showed that the highest concentration exposures were mainly concentrated in urban areas with a dense population. Flow variations controlled the temporal distribution characteristics of antibiotics via the dilution effect, and the concentrations of antibiotics in the dry season were 3.1 times higher than those in the wet season. The median concentrations of norfloxacin and erythromycin ranged from 111.36 ng/L to 592.33 ng/L and 106.63 ng/L to 563.01 ng/L, respectively, which both posed a high risk to cyanobacteria and a medium risk to spreading antibiotic resistance. Scenario analysis further demonstrated that high removal efficiencies of these antibiotics can considerably reduce the potential ecotoxicity risks and bacterial resistance selection. The developed methodology for predicting the distribution and risk of antibiotics was suitable for the risk assessment and control strategy of human- and livestock-sourced pollutants.

Antibiotics and antimycotics in waste water treatment plants: Concentrations, removal efficiency, spatial and temporal variations, prediction, and ecological risk assessment.

For investigating the spatial, temporal variations and assessing ecological risk of 10 antibiotics and 6 antimycotics, influent sewage water and treated effluent were collected during three different seasons in 19 waste water treatment plants of Tianjin. High performance liquid chromatography tandem mass spectrometry was used to analyze 16 substances. The concentration range of influent samples was not detected (nd) -547.94 ng/L and the concentration range of effluent samples was nd-52.97 ng/L. By calculating the removal efficiency, it was found that Ciprofloxacin (CIP), Ofloxacin (OFL) and Clotrimazole (CTR) were effectively removed. There were significant spatial and temporal differences, the concentration in the dry season was evidently higher than that in the wet and normal seasons, and the northeast was lower than that in the northwest and southeast. By establishing a data set of influent and effluent, the priority features were extracted by feature engineering, which were temperature and NH3-N. Under the condition of ensuring the best performance of the models, the influent model with 9 features and the effluent model with 4 features were established, and the quantitative relationship between the above features and concentration was obtained through partial dependence analysis. Except for Moxifloxacin (MOX), Norfloxacin (NOR) and OFL in the influent samples, the RQ values for other antibiotics and antimycotics were less than 0.1. Among the effluent samples, only NOR had an RQ value greater than 0.1, and OFL, MOX, and Pefloxacin (PEF) had RQ values between 0.01 and 0.1. Comparing the observations and predictions individual RQ values, the predictions were ideal and matched the observations. This work effectively assessed environmental impact and provided a valuable reference for evaluating antibiotics and antimycotics ecological toxicity.