Fluoroquinolones In Water Research Articles

Low flow-resistance solid phase extraction of fluoroquinolones in water and food samples by high-pressure wet spinning porous polyimide microfibers

In this work, porous polyimide microfibers (PI-μF) were prepared by high-pressure wet spinning method, and successfully applied as adsorbents for solid phase extraction (SPE) of fluoroquinolones (FQs) in water and food samples. The PI-μFs of ∼10, 25, 50, 100 μm in diameter could be controlled by the inner diameter of quartz capillary nozzles. The flow resistance of SPE cartridges packed with 10 μm PI microfiber (10-PI-μF) and 25-PI-μF was comparable to or even lower than that of commercial SPE cartridges, while the flow resistance of 50-PI-μF and 100-PI-μF SPE cartridges was increased obviously due to tiny broken pieces. The 10-PI-μF and 25-PI-μF have a specific surface area of 102 m2 g−1 and 76 m2 g−1, mesopores of 22–32 nm, and large breakthrough volume of 110 mL/5 mg and 85 mL/5 mg for FQs, while the 50-PI-μF and 100-PI-μF had much lower specific surface area and hardly had retention for FQs. FQs from tap water, egg and milk samples were then extracted by PI-μF SPE, and analyzed by high performance liquid chromatography-fluorescence detector (HPLC-FLD). SPE parameters as type of elution solvent, elution solvent volume, pH value of sample solution, flow rate of sample solution, and breakthrough volume were first optimized in detail. Under the optimal conditions, the PI-μF SPE/HPLC-FLD method showed high recoveries (96.8%–107%), wide linearity (0.05–50 μg L−1, or 0.01–10 μg L−1), high determination coefficients (R2 ≥0.9992), and low limits of detection (LODs, 0.005–0.014 μg L−1). For the real tap water, egg and milk samples, the recoveries and RSDs were 81–119% and 0.8–9.8%, respectively. The results show that porous microfiber up to 25 μm in diameter is a promising solid-phase extraction adsorbent with the lowest flow resistance that can be used for trace organic pollutants in water and food samples.

Methodological Approaches to Determination of Antibiotics in Water at the Level of Hygienic Standards Using High-Performance Liquid Chromatography–Mass Spectrometry

Introduction: The use of antibiotics in medicine and veterinary medicine has led to their accumulation in the natural environment, including source water, and antimicrobial resistance of certain types of bacteria. The development of methods for analyzing antibiotics in aquatic environments is relevant for ensuring tap water quality control at the level of hygienic standards, as well as for studying the process of development and spread of antibiotic resistance. The purpose of the study is to develop a method for determining such antibiotics as macrolides, penicillins, and fluoroquinolones in water at the level of hygienic standards using HPLC/MS-MS. Materials and methods: To elaborate the method, testing was done by HPLC/MS-MS using a liquid chromatograph with a triple quadrupole mass spectrometer. Extraction of antibiotics from various types of water samples (tap, natural) was carried out by solid-phase extraction. Results: We have developed a selective and highly sensitive method for the determination of eight antibiotics in water samples. The extraction efficiency for analytes ranged from 72 to 100 % and measured concentrations – from 0.25 to 2.50 of hygienic standards when analyzing 10 cm3 water samples; the relative error in determining antibiotics in water samples without concentration was 20–24 %, and 24–34 % in case of concentration on Oasis® HLB sorbent. Discussion: Approaches to developing a method for quantification of antibiotics of the penicillin, macrolide and quinolone classes in water by HPLC/MS-MS using solid-phase extraction for sample preparation are considered. The results are consistent with the data of scientific, technical and methodological literature. The advantages of this method include shorter sample preparation time, high sensitivity, and a small sample size. Study limitations: The main limitations are a short sampling period and the insufficient number of water samples tested. Expanding the list of surveyed water bodies on different territories may become a direction for further research to assess the content of antibiotics in aquatic environments. Conclusion: Our method can be used in hygienic studies of residual amounts of antibiotics to assess source water quality.

Occurrence, Bioaccumulation, Metabolism and Ecotoxicity of Fluoroquinolones in the Aquatic Environment: A Review.

In recent years, there has been growing concern about antibiotic contamination in water bodies, particularly the widespread presence of fluoroquinolones (FQs), which pose a serious threat to ecosystems due to their extensive use and the phenomenon of "pseudo-persistence". This article provides a comprehensive review of the literature on FQs in water bodies, summarizing and analyzing contamination levels of FQs in global surface water over the past three years, as well as the bioaccumulation and metabolism patterns of FQs in aquatic organisms, their ecological toxicity, and the influencing factors. The results show that FQs contamination is widespread in surface water across the surveyed 32 countries, with ciprofloxacin and norfloxacin being the most heavy contaminants. Furthermore, contamination levels are generally higher in developing and developed countries. It has been observed that compound types, species, and environmental factors influence the bioaccumulation, metabolism, and toxicity of FQs in aquatic organisms. FQs tend to accumulate more in organisms with higher lipid content, and toxicity experiments have shown that FQs exhibit the highest toxicity to bacteria and the weakest toxicity to mollusk. This article summarizes and analyzes the current research status and shortcomings of FQs, providing guidance and theoretical support for future research directions.

Coupled multimedia fate and bioaccumulation models for predicting fate of florfenicol and fluoroquinolones in water and fish organs in the seasonal ice-sealed reservoir

Ice formation in reservoirs could promote the accumulation of antibiotics in fish, potentially leading to elevated concentrations in fish muscles, kidneys, and livers. However, for the seasonal ice-sealed reservoirs, antibiotic sampling and detecting conditions in water and fish are normally limited by the ice cover. Additionally, previous studies on the prediction of antibiotics accumulated in seasonal ice-sealed reservoir fish are scarce. This study presents a coupled model incorporating a multimedia fate model and a bioaccumulation model to predict antibiotic fate in water and the muscles, kidneys, and livers of fish in seasonal ice-sealed reservoirs. Prediction concentrations of florfenicol were higher than those of ofloxacin and norfloxacin in both water and fish from the seasonal ice-sealed reservoir. Log bioaccumulation factors of antibiotics in Cyprinus carpio and Hypophthalmichthys nobilis in January 2021 were higher than those in October 2020 by 21.5% and 12.6%, respectively. Antibiotics mean transfer fluxes from water to fish muscles, kidneys, and livers increased owing to the reservoir ice-cover formation date advancing by 13.0%, 77.1%, and 61.0%, respectively. This work provides a modeling tool for investigating the fate and mass transfer flux of antibiotics in biological and environmental phases in seasonal ice-sealed reservoirs.

The Ultratrace Determination of Fluoroquinolones in River Water Samples by an Online Solid-Phase Extraction Method Using a Molecularly Imprinted Polymer as a Selective Sorbent.

Fluoroquinolones (FQs) are broad-spectrum antibiotics widely used to treat animal and human infections. The use of FQs in these activities has increased the presence of antibiotics in wastewater and food, triggering antimicrobial resistance, which has severe consequences for human health. The detection of antibiotics residues in water and food samples has attracted much attention. Herein, we report the development of a highly sensitive online solid-phase extraction methodology based on a selective molecularly imprinted polymer (MIP) and fluorescent detection (HPLC-FLD) for the determination of FQs in water at low ng L−1 level concentration. Under the optimal conditions, good linearity was obtained ranging from 0.7 to 666 ng L−1 for 7 FQs, achieving limits of detection (LOD) in the low ng L−1 level and excellent precision. Recoveries ranged between 54 and 118% (RSD < 17%) for all the FQs tested. The method was applied to determining FQs in river water. These results demonstrated that the developed method is highly sensitive and selective.

Nanoporous Polyimide Microspheres Solid Phase Extraction Coupled to Liquid Chromatography with Fluorescence Detection to Determine Fluoroquinolones in Water and Food Samples

Nanoporous Polyimide Microspheres Solid Phase Extraction Coupled to Liquid Chromatography with Fluorescence Detection to Determine Fluoroquinolones in Water and Food Samples

Enhanced photo-Fenton degradation of fluoroquinolones in water assisted by a 3D composite sponge complexed with a S-scheme MoS2/Bi2S3/BiVO4 ternary photocatalyst

A constructed MoS2/Bi2S3/BiVO4 ternary photocatalyst(MBB) mainly with a S-scheme heterostructure was loaded on a 3D lignosulfonate modified poly(vinyl formal) sponge to obtain a novel composite sponge(PLS-MBB) with an enhanced performance in synergistic adsorption and photo-Fenton degradation of various fluoroquinolones(FQs) in water. The synergistic adsorption and photocatalysis of PLS-MBB notably improved the applicable pH from 2.0 to 9.0 and reduced the dosage of Fe2+ to 0.014 mmol/L in Fenton reaction, which could achieve the degradation efficiency of 92.8 % for FQs within 60.0 min at pH 6.0. The photo-generated electrons by MBB and the redox transformation of Mo(IV)/Mo(VI) and Bi(III)/Bi(V) accelerated the conversion of Fe3+ to Fe2+; besides, the efficient adsorption of FQs on the sponge carrier promoted the surface degradation in solution, thereby causing an enhanced photo-Fenton reaction. This work provided a novel strategy to improve photo-Fenton reaction and accordingly fabricated a talented material for effective removal of organic contaminants in water.

Fabrication of 3D lignosulfonate composited sponges impregnated by BiVO4/polyaniline/Ag ternary photocatalyst for synergistic adsorption-photodegradation of fluoroquinolones in water

In this work, a 3D lignosulfonate composited poly(vinyl formal) (PVF) sponge impregnated by BiVO4/polyaniline (PANI)/Ag ternary photocatalyst (PLS-BiVO4/PANI/Ag) was designed and fabricated. The synergistic adsorption-photodegradation of five fluoroquinolones (FQs) antibiotics onto PLS-BiVO4/PANI/Ag was investigated. Incorporating lignosulfonate as a carrier on PVF sponge improved its structural properties and enhanced its adsorption performance toward FQs. The BiVO4/PANI/Ag ternary photocatalyst was well-dispersed and tightly bound to the composited sponge, thus it efficiently degraded the adsorbed FQs through surface photodegradation. PLS-BiVO4/PANI/Ag achieved >90% removal efficiency for all examined FQs within 2.0 h in a batch system, while it maintained a steady 80% removal efficiency for 30.0 h in a continuous dynamic treatment system. Photoelectric characterizations and ESR results showed that BiVO4/PANI/Ag was consistent with the type II heterostructure and effectively improved the utilization of visible light and the separation of photogenerated electron-hole pairs. The hole was the dominant active species in the degradation of FQs, while the main degradation pathways included defluorination, decarboxylation and destruction of piperazine ring. The prepared composited sponge is thus characterized by its high performance, convenient operation, eco-friendliness, and practicality in real water treatment systems since it undergoes self-purification and is easily recovered from water without mass loss.

Comparative Study of Hyper-crosslinked Polymer-Solid Phase Microextraction and Stir Bar Fabric Phase Sorptive Extraction for Simultaneous Determination of Fluoroquinolones in Water

Comparative Study of Hyper-crosslinked Polymer-Solid Phase Microextraction and Stir Bar Fabric Phase Sorptive Extraction for Simultaneous Determination of Fluoroquinolones in Water

Hierarchically Z-scheme photocatalyst of {0 1 0}BiVO4/Ag/CdS with enhanced performance in synergistic adsorption-photodegradation of fluoroquinolones in water

In this work, the sheet-like BiVO4 with a higher exposure ratio of {010} facets was synthesized by the addition of TiCl3, and the ratio of (040)/(011) on {010}BiVO4 was 2.85 times higher than that of normal decahedral BiVO4. Accordingly, the {010}BiVO4/Ag/CdS all-solid-state Z-scheme heterojunction was further constructed by photoreduction of Ag and chemical deposition of CdS on the well prepared {010}BiVO4 successively. The performance and mechanism of {010}BiVO4/Ag/CdS in synergistic adsorption-photodegradation of fluoroquinolones (FQs) from water were investigated in detail. The adsorption-photodegradation could be divided into three processes: adsorption, surface degradation, and solution degradation, with the rate constants of 0.118, 0.029, and 0.012 min−1, respectively. Accordingly, the adsorption was a rapid process due to the combined CdS in this composited photocatalyst had a high affinity to FQs to achieve an adsorption equilibrium on the surfaces<30.0 min. Besides, {010}BiVO4/Ag/CdS had a better separation efficiency of photogenerated electron-hole pairs than BiVO4/Ag/CdS, because the enriched {010} facets of {010}BiVO4 caused more BiVO4/Ag/CdS ternary structure formed, and>90% photodegradation efficiency for five FQs (C0 = 0.062 mmol/L) was thus obtained within 60.0 min. The radical trapping and EPR results showed that holes and superoxide radicals were the main active species for FQs photodegradation. In summary, {010}BiVO4/Ag/CdS achieved an enhanced performance in synergistic adsorption and photodegradation of organic contaminants from water, and a talented photocatalyst was thus provided in water and wastewater treatment.

Macro-microporous zeolitic imidazole framework-8/cellulose aerogel for semi-automated pipette tip solid phase extraction of fluoroquinolones in water

In this study, Zeolitic Imidazole Framework-8/cellulose aerogel (ZIF-8/CA) hybrid was successfully fabricated through a simple doping method and ZIF-8 acted as the major component for adsorption. In order to elucidate the adsorption mechanism deeply, molecular simulation was adopted to the expound the interaction modes between ZIF-8 and the fluoroquinolones (FQs). ZIF-8/CA was used as the adsorbent for semi-automated pipette tip solid phase extraction (PT-SPE). In combination with high performance liquid chromatography tandem fluorescence detector (HPLC-FLD), the established method was successfully employed to determine trace amount of FQs in water samples. Extraction parameters such as the content of ZIF-8, pH of sample solution, volume of sample, flow rate of sampling, type and volume of elution solvent were investigated. Under the optimized conditions, satisfactory linearity was achieved with the correlation coefficient (R2) ranging from 0.9954 to 0.9992. The limits of detection were in the range of 0.337–1.707 ng L−1. And the recoveries varied from 75.9% to 96.8% with RSD less than 8.0%. The established method was demonstrated to be sensitive, efficient and convenient.

Occurrence, Distribution, and Ecological Risk of Fluoroquinolones in Rivers and Wastewaters.

The use of fluoroquinolones for the treatment of infections in humans and animals has increased in Argentina, and they can be found in large amounts in water bodies. The present study investigated the occurrence and associated ecological risk of 5 fluoroquinolones in rivers and farm wastewaters of San Luis, Santa Fe, Córdoba, Entre Ríos, and Buenos Aires provinces of Argentina by high-performance liquid chromatography coupled to fast-scanning fluorescence detection and ultra-high-performance liquid chromatography coupled to triple quadrupole mass spectrometry detection. The maximum concentrations of ciprofloxacin, enrofloxacin, ofloxacin, enoxacin, and difloxacin found in wastewater were 1.14, 11.9, 1.78, 22.1, and 14.2 μg L-1 , respectively. In the case of river samples, only enrofloxacin was found, at a concentration of 0.97 μg L-1 . The individual risk of aquatic organisms associated with water pollution due to fluoroquinolones was higher in bacteria, cyanobacteria, algae, plants, and anurans than in crustaceae and fish, with, in some cases, risk quotients >1. The proportion of samples classified as high risk was 87.5% for ofloxacin, 63.5% for enrofloxacin, 57.1% for ciprofloxacin, and 25% for enoxacin. Our results suggest that the prevalence of fluoroquinolones in water could be potentially risky for the aquatic ecosystem, and harmful to biodiversity. Environ Toxicol Chem 2019;38:2305-2313. © 2019 SETAC.

Preparation of highly fluorinated and boron-rich adsorbent for magnetic solid-phase extraction of fluoroquinolones in water and milk samples

Effective extraction is an indispensable procedure for the sensitive analysis of fluoroquinolones (FQs) in complex samples. According to the molecular properties of FQs, a new highly fluorinated and boron-rich adsorbent (FBA) was synthesized and employed as the extraction phase of magnetic solid-phase extraction (MSPE). Results revealed that the prepared FBA displayed satisfactory extraction capability for FQs through fluorophilic and B–N coordination interactions. Besides, the synthesized FBA also exhibited strong magnetic responsiveness and good life-span. Under the most favorable conditions, the FBA/MSPE was combined with high-performance liquid chromatography with diode array detection (HPLC-DAD) to sensitively quantify trace levels of FQs in environmental water and milk samples. The developed approach showed good linearity within the studied concentration range, satisfactory precision and low limits of detection (0.0049–0.016 μg/L for water sample and 0.010–0.046 μg/kg for milk sample). In the analysis of target FQs in real samples, the recoveries of different fortified concentrations were in the ranges of 80.1–120% and 78.9–119% for water and milk samples, respectively. The relative standard deviations for reproducibility were all below 11%. The results well evidence that the introduced FBA/MSPE is a promising extraction technology for FQs, and the established FBA/MSPE-HPLC/DAD approach is suitable to measure low concentrations of FQs in water and milk samples.

Metal-organic framework-monolith composite-based in-tube solid phase microextraction on-line coupled to high-performance liquid chromatography-fluorescence detection for the highly sensitive monitoring of fluoroquinolones in water and food samples

In this study, a new metal-organic framework-monolith composite for in-tube solid phase microextraction phase (IT-SPME) of fluoroquinolones (FQs) was prepared. 4-Vinylbenzoic acid was copolymerized with ethylenedimethacrylate in a fused silica capillary to form porous monolith. After that, zeolitic imidazolate frameworks (ZIF-8) were synthesized in situ within the pores and the surface of the monolith by controlled layer-by-layer self-assembly of Zn2+ and imidazole. The introduction of ZIF-8 enhanced the surface area of monolith composite, and thus, improving the extraction performance of IT-SPME for FQs obviously. Under the optimized conditions, a highly sensitive method for the monitoring of FQs residue in water and honey samples was developed by the on-line combination of IT-SPME with high-performance liquid chromatography with fluorescence detection (HPLC-FLD). The limits of detection (S/N = 3) for the targeted FQs in water and honey samples were as low as 0.14–0.61 ng/L and 0.39–1.1 ng/L, respectively. The relative standard deviations (RSDs) for intra-day and inter-day assay variability were less than 10% in all samples. The established on-line IT-SPME-HPLC-FLD was successfully used to detect ultra-trace FQs in environmental water and honey samples. Recoveries at different spiked concentrations ranged from 80.1% to 119% and 80.2–117% for water and honey samples, respectively, with satisfactory reproducibility. Compared to up-to-date reported methods, the proposed approach exhibits some features such as high sensitivity, convenience, partial automation, low consumptions of sample and solvent.

Influence of chemical speciation on photochemical transformation of three fluoroquinolones (FQs) in water: Kinetics, mechanism, and toxicity of photolysis products

This study investigated the contribution of direct, indirect, and self-sensitized photolysis to the photochemical fate of three model fluoroquinolones (FQs), i.e., lomefloxacin (LOM), norfloxacin (NOR), and ofloxacin (OFL), and demonstrated the influence of chemical speciation on their photodegradation behavior, a topic that has received relatively little attention. Results suggest that these FQs in water transformed mainly via direct photolysis, while hydroxyl radical played a key role in their indirect and self-sensitized photolysis. Chemical speciation of such zwitterionic compounds significantly affected the kinetics of their phototransformation, with the quantum yields of photodegradation decreased in the order of zwitterionic (FQsH) > anionic (FQs−) > cationic (FQsH2+). The photodegradation pathways of FQs depended on both their structures and chemical speciation. Defluorination for LOM in C-8 and NOR in C-6 was more significant when they were present in zwitterionic form than in the other forms. Cationic FQs underwent direct piperazinyl ring cleavage, and zwitterionic ones underwent piperazinyl ring oxidation, while the degradation pathway of piperazinyl ring for FQs in anionic form was structure dependent. Decarboxylation for zwitterionic FQs occurred more slowly compared to both cationic and anionic ones, and the FQs bearing electron-donating groups in C-8 position degraded more easily in cationic form than the anionic ones, while the opposite was true for the FQs without such a group in C-8 position. Results of Vibrio fischeri bioluminescence inhibition tests showed the toxicity of zwitterionic NOR and OFL significantly decreased after photodegradation, while the degradation products of LOM exhibited greater toxicity. These findings indicate that chemical speciation of zwitterionic compounds could affect the kinetics and pathways of their photochemical transformation, and thus have important implications on their fate and risk in aquatic environment.

In-tube magnetic solid phase microextraction of some fluoroquinolones based on the use of sodium dodecyl sulfate coated Fe3O4 nanoparticles packed tube

In-tube magnetic solid phase microextraction (in-tube MSPME) of fluoroquinolones from water and urine samples based on the use of sodium dodecyl sulfate (SDS) coated Fe3O4 nanoparticles packed tube has been reported. After the preparation of Fe3O4 nanoparticles (NPs) by a batch synthesis, these NPs were introduced into a stainless steel tube by a syringe and then a strong magnet was placed around the tube, so that the Fe3O4 NPs were remained in the tube and the tube was used in the in-tube SPME-HPLC/UV for the analysis of fluoroquinolones in water and urine samples. Plackett–Burman design was employed for screening the variables significantly affecting the extraction efficiency. Then, the significant factors were more investigated by Box–Behnken design. Calibration curves were linear (R2>0.990) in the range of 0.1–1000μgL−1 for ciprofloxacin (CIP) and 0.5–500μgL−1 for enrofloxacin (ENR) and ofloxacin (OFL), respectively. LODs for all studied fluoroquinolones ranged from 0.01 to 0.05μgL−1. The main advantages of this method were rapid and easy automation and analysis, short extraction time, high sensitivity, possibility of fully sorbent collection after analysis, wide linear range and no need to organic solvents in extraction.

Development of sensitive and reliable LC-MS/MS methods for the determination of three fluoroquinolones in water and fish tissue samples and preliminary environmental risk assessment of their presence in two rivers in northern Poland

Antibiotic consumption (e.g. fluoroquinolones (FQs)) and, as a consequence, their presence in the environment, have received a lot of attention in the last several years due to increasing numbers of diseases and infections that are becoming resistant to traditional treatments for both humans and animals. In addition, even though antibiotics are safe for human and veterinary usage, ecosystems may be exposed to these substances. In this study, analytical methods for determining enrofloxacin (ENR), norfloxacin (NOR) and ciprofloxacin (CIP) in water samples and fish tissue based on the LC-MS/MS technique were developed and validated. As there is no data available concerning the risks posed by antibiotics in Poland, the proposed methods were applied for monitoring drug presence in environmental samples collected from two rivers in northern Poland. Evaluations of the ecotoxicity of ENR, NOR and CIP towards four different species of aquatic organisms: marine bacteria (Vibrio fischeri), green algae (Scenedesmus vacuolatus), duckweed (Lemna minor) and crustacean (Daphnia magna), were also carried out. All the investigated compounds were detected at least once in the survey. NOR was found to be the most ubiquitous drug with concentrations of up to 442.8ngL−1. Moreover, it was established that L. minor is the most sensitive species to the investigated drugs (EC50NOR=0.13mgL−1, EC50ENR=0.22mgL−1 and EC50CIP=0.34mgL−1). The calculated risk quotient (RQ) values confirmed that the concentrations of the investigated FQs in the environmental samples were at a level of moderate environmental risk (1<RO≤10), however, for CIP they were found to be closer to a level of high environmental risk (RQCIP=8.1).

Salting-out induced liquid–liquid microextraction based on the system of acetonitrile/magnesium sulfate for trace-level quantitative analysis of fluoroquinolones in water, food and biological matrices by high-performance liquid chromatography with a fluorescence detector

A convenient, economical SILLME method coupled with HPLC/FLD for sample preparation, extraction and trace-level quantitative determination of fluoroquinolones is reported.