Even though Ibuprofen is one of the most studied pharmaceutical in the aquatic environment, there is still a lack of information about its fate and the generation of different transformation products ...along wastewater treatment plants (WWTPs). Ibuprofen biotransformation products can be generated by human metabolism or by microorganisms present in WWTPs and in natural waters, soils, and sediments, which increase the probability to find them in environment. In this work, the presence of ibuprofen and its main metabolites: ibuprofen carboxylic acid (CBX IBU), 2-hydroxylated ibuprofen (2-OH IBU) and 1-hydroxylated ibuprofen (1-OH IBU), was monitored quantitatively along the biodegradation processes occurring in different batch activated sludge (BAS) experiments under different working conditions. Total ibuprofen removal, achieved in almost all the experiments, was related in part to the formation of the metabolites mentioned. Another ibuprofen metabolite, 1,2-dihydroxy ibuprofen, was detected in BAS experiments for the first time. The metabolites 2-OH IBU and 1-OH IBU remained in solution at the end of ibuprofen biodegradation experiments whereas CBX IBU disappeared faster than hydroxylated metabolites. In addition, also the biodegradation of 1-OH IBU, 2-OH IBU and CBX IBU was evaluated in batch experiments: CBX IBU removal occurred at the highest rate followed by IBU, 2-OH IBU, and 1-OH IBU, which exhibited the lowest removal rate. Finally, Ibuprofen and ibuprofen metabolites were monitored in sewage and natural water samples, where they were found at higher levels than expected: the maximum concentration in influent wastewater samples were 13.74, 5.8, 38.4, 94.0μg/L for IBU, 1-OH IBU, CBX IBU and 2-OH IBU respectively; whereas maximum levels in effluent wastewater samples were 1.9, 1.4, 10.7, 5.9μg/L for IBU, 1-OH IBU, CBX IBU and 2-OH IBU respectively. High levels of the compounds were also found in river samples, in particular for CBX IBU, which was detected up to 3.9μg/L.
► Fast quantification of ibuprofen and its metabolites in batch studies, real wastewater and river samples ► First detection of 1,2-dihydroxy ibuprofen in activated sludge batch experiments ► First removal study of ibuprofen metabolites in activated sludge batch experiments ► Very high levels of metabolites in comparison to ibuprofen in real influent, effluent and river water
Strategies for sample preparation, solid-phase extraction (SPE), clean-up, and detection conditions of an optimized solid-phase extraction-liquid chromatography/mass/mass spectrometry (SPE-LC/MS/MS) ...method for determining multi-residues of four classes of widely used antibiotics in pig farms, sulfonamides (SAs), fluoroquinolone (FQs), tetracycline (TCs) and chloramphenicol (CAP) were presented. The multi-residue analysis was used in MS analysis, selecting two precursor ions to produce ion transitions for each target compound. Samples of swine wastewater, lake water and groundwater collected from two pig farms in central China were used to test the applicability of the multi-residue analysis method. The average antibiotics concentrations in groundwater, lake water, final effluent and influent swine wastewater were, respectively, 1.6–8.6, 5.7–11.6, 7.9–1172.3 and 8.5–21692.7
ng
L
−1 in summer; respectively, 2.0–7.3, 6.7–11.7, 5.8–409.5 and 32.8–11276.6
ng
L
−1 in winter. The limits of quantification were 0.8–4.1, 1.4–5.5, 1.8–11.5 and 6.4–104.4
ng
L
−1, respectively, in groundwater, lake water, final effluent and influent swine wastewater. Results of multi-residue analysis of antibiotics in the samples indicate that SAs, FQs and TCs were widely used veterinary medicines in the pig farms. As compared with previous studies, higher elimination rates (more than 80%) of the antibiotics (except DC) were observed in effluent in this study. More detailed work is indispensable to investigate the fate and transport of antibiotics in the environment and to find out cost-effective approaches of removing antibiotics from swine wastewater and contaminated sites.
The presence of antibiotics in seafood for human consumption may pose a risk for consumers. A methodology for the analysis of antibiotics in seafood based on QuEChERS (quick, easy, cheap, effective, ...rugged, and safe) extraction, followed by detection and quantification using liquid chromatography coupled to mass spectrometry was developed. The analytical method was evaluated for the determination of 23 antibiotics (including parent compounds and some metabolites) in fish, mussels and clams. Recoveries ranged between 30% and 70% for most of the compounds and method detection and quantification limits (MDLs and MQLs) were between 0.01 and 0.31 ng/g dry weigh (dw) and 0.02–1.03 ng/g (dw) respectively. Real seafood samples were analysed using this method. Nine antibiotics were found at levels above MDLs; however none of them exceed the maximum residue limits (MRL) established by the authorities. Tetracycline was the most ubiquitous compound, presenting also the highest concentration: 5.63 ng/g (dw) in fish from Netherlands. In addition, an alternative technique based on microbial growth inhibition was explored as semiquantitative detection method of antibiotics in seafood. This methodology could be applied as a fast screening technique for the detection of macrolides and β-lactams in seafood but further research is needed for other antibiotics families.
•A methodology was developed for the detection of 23 antibiotics in seafood.•QuEChERS extraction followed by UHPLC-MS/MS showed an optimal performance.•Nine antibiotics were detected in real seafood, all of them with levels below MRL.•A microbial inhibition test allowed a preliminary detection of macrolides/β-lactams.
Four new thymol‐based ternary deep eutectic solvents were prepared and evaluated as the extractive phase in air‐bubbles assisted dispersive liquid‐liquid microextraction for extraction of ...tetracycline, doxycycline, and oxytetracycline from the water before high‐performance liquid chromatography. The maximum extraction efficiencies were obtained using 400 μL of choline chloride:thymol:nonanoic acid in the molar ratio of 1:2:2 at pH = 5. The solvent was characterized by FTIR and NMR spectroscopy. The hydrophobicity of the deep eutectic solvent and its effect on the pH of water samples after mixing was also studied. Besides, the extraction efficiency of the ternary deep eutectic solvent was compared with that of two binary thymol‐based deep eutectic solvents, including choline chloride:thymol and thymol:nonanoic acid at the same conditions. Under optimal conditions, limits of detection and quantification were 1.2–8.0 and 3.8–26.6 μg/L, respectively. The linear ranges were 18.2–500 μg/L for oxytetracycline, 26.6–500 μg/L for tetracycline, and 3.8–500 μg/L for doxycycline with the determination coefficients > 0.9912. Intra‐ and inter‐day relative standard deviations were 1.2–3.8 and 7.7–11.2%, respectively. The developed method was applied to the analysis of tetracyclines in unspiked and spiked environmental water samples, and the obtained recoveries were 74.5–95.4% with relative standard deviations of 1.2–4.0%.
•The core-shell Fe3O4@MoS2 nanocomposite was synthesized and characterized.•The Fe3O4@MoS2 was first used as adsorbent for magnetic solid-phase extraction.•The nanocomposites have remarkable ...extraction capability toward SAs.•The method was successfully applied in determination of SAs.
A molybdenum disulfide(MoS2)-based core-shell magnetic nanocomposite (Fe3O4@MoS2) was synthesized by the stepwise hydrothermal method. Two-dimension ultrathin MoS2 sheets with a thickness of approximately 20 nm were grown in situ on the surface of Fe3O4 (∼200 nm). They were employed as an adsorbent for the magnetic solid-phase extraction (MSPE) of sulfonamide antibiotics (SAs) from water samples. High-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) was used for SA quantitation. Extraction parameters, including the pH effect, amount of Fe3O4@MoS2, extraction time, temperature, and desorption conditions, were systematically investigated. The electrostatic interaction between the positively charged SAs and negatively charged MoS2 nanoparticles in the optimal extraction conditions enhanced the adsorption of SAs on the sorbent surface. Under chosen conditions, the proposed strategy achieved wide linear range of 1.0–1000 ng·L−1 SAs, low limits of detection (LOD, 0.20–1.15 ng·L−1, S/N = 3:1), good trueness (recoveries between 85.50–111.5%), satisfactory repeatability and reproducibility (relative standard deviation, <10%, n = 5), and excellent recoveries between 80.20% and 108.6% for SAs determination in spiked waste water samples. The proposed strategy was validated and successfully applied for the analysis of water, milk, pork meat and fish meat. The nanocomposites, which have the combined advantages of magnetic separation and high adsorption affinity toward SAs, are a promising sorbent for antibiotics extraction from real samples.
•Synthesis of dual-template molecular imprinted polymer (DMIP) for fluoroquinolones.•Studying its recognition mechanism by using computational simulation software.•Preparation of a DMIP based stir ...bar sorptive extraction method (SBSE).•Optimization of absorption condition, extraction time, desorption solvent and time.•Application of DMIP-SBSE to detect the residues of nine fluoroquinolones in meat.
In this study, a dual-template molecularly imprinted polymer-coated stir bar capable of recognizing nine fluoroquinolone drugs was prepared. Its recognition abilities for fluoroquinolones and other drugs were studied by using computational simulation method. Results showed that the shape and volume of the imprinted cavities were responsible for the polymer’s recognition performance. After optimization of several important parameters, a stir-bar-sorptive-extraction method was developed that was combined with high performance liquid chromatography for determination of the nine drugs in meat. The stir bar showed high enrichment factors (33–47 folds), high capture capacities (4640–4950ng) and high recoveries (>90%) for the nine drugs, and could be reused for thirty times. The limits of detection for the nine drugs were in the range of 0.1–0.3ngg−1, and the recoveries from the fortified blank meat were in the range of 67.4%–99.0%. Therefore, this method could be used as a simple, rapid and specific tool for routine detection of residual fluoroquinolones in meat.
► Fe3O4@MIP nanoparticles for water-soluble pefloxacin mesylate were prepared via ATRP. ► Fe3O4@MIP exhibited the excellent recognition ability to PEF-M in aqueous media. ► Fe3O4@MIP nanoparticles ...were used to selectively enrich PEF-M from egg samples. ► Imprinting water-soluble small molecules using high polar media via si-ATRP.
The novel superparamagnetic surface molecularly imprinted Fe3O4@MIP nanoparticles for water-soluble pefloxacin mesylate (PEF-M) were prepared via surface initiated atom transfer radical polymerization (si-ATRP). The binary mixture of methanol and water was selected as the polar solvents for fabricating PEF-M imprinted MIPs. The Fe3O4@MIP exhibited high saturation magnetization of 41.4emu/g leading to the fast separation. The adsorption behaviors indicated that the Fe3O4@MIP nanoparticles possessed specific recognition and high affinity towards template PEF-M in aqueous media. Moreover, Fe3O4@MIP nanoparticles were directly used to selectively enrich PEF-M from egg samples. By RP-HPLC analysis, the recoveries of PEF-M were obtained as 92.8–96.5% with relative standard division of 2.4–4.0%.
Drugs are used in veterinary medicine to prevent or treat animal diseases. When rationally administered to livestock following Good Veterinary Practices (GVP), they greatly contribute to improving ...the production of food of animal origin. Since humans can be exposed chronically to veterinary drugs through the diet, residues in food are evaluated for effects following chronic exposures. Parameters such as an acceptable daily intake (ADI), the no-observed-adverse-effect level (NOAEL), maximum residue limits (MRLs), and the withdrawal periods (WPs) are determined for each drug used in livestock. Drug residues in food exceeding the MRLs usually appear when failing the GVP application. Different factors related either to the treated animal or to the type of drug administration, and even the type of cooking can affect the level of residues in edible tissues. Residues above the MRLs can have a diverse negative impact, mainly on the consumer’s health, and favor antimicrobial resistance (AMR). Drug residue monitoring programmes are crucial to ensure that prohibited or authorized substances do not exceed MRLs. This comprehensive review article addresses different aspects of drug residues in edible tissues produced as food for human consumption and provides relevant information contributing to rational pharmacotherapy in food-producing animals.
•A novel aptamer functionalized magnetic adsorbent was developed for selective enrichment of three amphenicols in complex food matrix.•Dispersive solid phase extraction method coupling with the ...adsorbent was employed for detection 0.1ng/ml of amphenicols in milk.•This assay is environmentally friendly and time-saving due to without using organic reagent and purifying.
In this work, a novel aptamer functionalized magnetic adsorbent was developed and combined with magnetic dispersive solid phase extraction (MDSPE) for selective enrichment of several amphenicol antibiotics residues (chloramphenicol(CAP), thiamphenicol(TAP) and florphenicol(FF)) in foodstuff then determined by High Performance Liquid Chromatography (HPLC)-Diode array detector(DAD). Firstly, a magnetic silica-coated Fe3O4 microsphere(Fe3O4@SiO2) was synthetized by sol-gel method, then it was functionalized by amino groups through 3-Aminopropyltriethoxysilane (APTES) reagent to form Fe3O4@SiO2-NH2; Thirdly, the amino group on Fe3O4@SiO2-NH2 was transferred to carboxylic group via the succinic anhydride to form Fe3O4@SiO2-COOH. Finally a kind of DNA aptamer with amino group which can simultaneously recognize CAP, TAP, FF, was functionalized on Fe3O4@SiO2-COOH through adding the EDC/sulfo-NHS coupling reagent (Fe3O4@SiO2@Apt). Therefore, a very stable and useful adsorbent was synthesized for the detection of chloramphenicol series antibiotics. This adsorbent can specifically and simultaneously recognize and enrich CAP, TAP, and FF with high adsorption amount from some complicated food matrix, e.g. milk based on the high affinity of aptamer towards the analytes. The saturated extraction capacities for CAP, TAP and FF by the adsorbent were 2.82, 2.56, 2.72μg/g (mass of target/adsorbent)respectively and the enrichment folds were more than 100 times. Afterwards, the target analytes were washed away by pH 8.5 0.1M Tris-HCl buffer solution and detected by HPLC-DAD. The parameters including extraction temperature, extraction capacity, extraction & desorption pH, extraction & desorption time were investigated. With the optimized conditions, the limits of detection (LOD) and limits of quantitation (LOQ) were 0.12–0.17ng/ml and 0.40–0.55ng/ml for the amphenicols in milk. The adsorbent also has good reproducibility for extraction which can be reused at least for 60 cycles with the recovery over 80% (Fig. S2). The MDSPE combined with HPLC-DAD detection possessed the advantages of high selectivity, extraction capacity and very convenient for magnetic separation. In addition, this method is environment friendly and employed no organic solution in the period of pretreatment and extracting. It is a universal platform which can be extended to selective enrichment other organic pollutants residues if changing the modified aptamers.
Although antibiotics have been used in large quantities for some decades, until recently the existence of these substances in the environment has received little notice. It is only in recent years ...that a more complex investigation of antibiotic substances has been undertaken in order to permit an assessment of the environmental risks they may pose. Within the last decade an increasing number of studies covering antibiotic input, occurrence, fate and effects have been published, but there is still a lack of understanding and knowledge about antibiotics in the aquatic environment despite the numerous studies performed. This review addresses the present state of knowledge concerning the input, occurrence, fate and effects of antibiotics in the environment. It brings up important questions that are still open, and addresses some significant issues which must be tackled in the future for a better understanding of the behavior of antibiotics in the environment, as well as the risks associated with their occurrence. Questions related to resistance in the environment that may be caused by antibiotics will be addressed in the second part.
PDF
