Ziarrusta Haizea, Val Nahia, Dominguez Haizea, Mijangos Leire, Prieto Ailette, Usobiaga Aresatz, Etxebarria Nestor, Zuloaga Olatz, Olivares Maitane
Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country (UPV/EHU), PK. 644, 48080, Bilbao, Basque Country, Spain.
Research Centre for Experimental Marine Biology and Biotechnology (PIE), University of the Basque Country (UPV/ EHU), Areatza Pasealekua, 48620, Plentzia, Basque Country, Spain.
Anal Bioanal Chem. 2017 Nov;409(27):6359-6370. doi: 10.1007/s00216-017-0575-4. Epub 2017 Aug 29.
This work describes the optimization, validation, and application in real samples of accurate and precise analytical methods to determine ten fluoroquinolones (FQs) (norfloxacin, enoxacin, pefloxacin, ofloxacin, levofloxacin, ciprofloxacin, danofloxacin, lomefloxacin, enrofloxacin, and sparfloxacin) in different environmental matrices, such as water (estuarine, seawater, and wastewater treatment plant effluent), fish tissues (muscle and liver), and fish biofluids (plasma and bile). The analysis step performed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) was fully optimized to improve the separation and detection steps. The extraction of analytes from fish tissues was accomplished using focused ultrasound solid-liquid extraction using methanol/acetic acid (95:5 v/v) as extractant. The preconcentration and clean-up steps were optimized in terms of extraction efficiency and cleanliness and the best strategy for each matrix was selected: (i) Oasis HLB for seawater and muscle, (ii) liquid-liquid extraction combined with Oasis HLB for the lipid-rich liver, (iii) the combination of Evolute-WAX and Oasis HLB for estuarine water and wastewater treatment plant effluent, and (iv) molecular imprinted polymers for biofluids. The methods afforded satisfactory apparent recoveries (80-126%) and repeatability (RSD < 15%), except for sparfloxacin, which showed a lack of correction with the available isotopically labeled surrogates ([H]-ciprofloxacin and [H]-enrofloxacin). Ciprofloxacin, norfloxacin, and ofloxacin were detected in both water and fish liver samples from the Biscay Coast at concentrations up to 278 ng/L and 4 ng/g, respectively. To the best of our knowledge, this work is one of the few analyzing up to ten FQs and in so many fish tissues and biofluids. Graphical abstract Determination of fluoroquinolones in different environmental matrices, such as water (estuarine, seawater, and wastewater treatment plant effluent), fish tissues (muscle and liver), and fish biofluids (plasma and bile).
本研究描述了准确、精密的分析方法在实际样品中的优化、验证及应用，该方法用于测定不同环境基质中的十种氟喹诺酮类药物（FQs）（诺氟沙星、依诺沙星、培氟沙星、氧氟沙星、左氧氟沙星、环丙沙星、达氟沙星、洛美沙星、恩诺沙星和司帕沙星），这些环境基质包括水（河口、海水和污水处理厂出水）、鱼组织（肌肉和肝脏）以及鱼生物流体（血浆和胆汁）。通过液相色谱 - 串联质谱（LC-MS/MS）进行的分析步骤得到了充分优化，以改进分离和检测步骤。使用甲醇/乙酸（95:5 v/v）作为萃取剂，通过聚焦超声固液萃取法从鱼组织中提取分析物。在萃取效率和清洁度方面对预浓缩和净化步骤进行了优化，并为每种基质选择了最佳策略：（i）用于海水和肌肉的Oasis HLB；（ii）用于富含脂质的肝脏的液液萃取结合Oasis HLB；（iii）用于河口和污水处理厂出水的Evolute-WAX和Oasis HLB的组合；（iv）用于生物流体的分子印迹聚合物。除司帕沙星外，该方法具有令人满意的表观回收率（80 - 126%）和重复性（RSD < 15%），司帕沙星与可用的同位素标记替代物（[H]-环丙沙星和[H]-恩诺沙星）缺乏校正。在比斯开湾海岸的水和鱼肝样品中分别检测到环丙沙星、诺氟沙星和氧氟沙星，浓度分别高达278 ng/L和4 ng/g。据我们所知，这项工作是为数不多的同时分析多达十种氟喹诺酮类药物以及多种鱼组织和生物流体的研究之一。图形摘要 测定不同环境基质中的氟喹诺酮类药物，如 水（河口、海水和污水处理厂出水）、鱼组织（肌肉和肝脏）以及鱼生物流体（血浆和胆汁）。
