Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country, P. K. 644, 48080, Bilbao, Spain; Laboratoire de Chimie Analytique Bio-inorganique et Environnement, Institut Pluridisciplinaire de Recherche sur l'Environnement et les Matériaux, CNRS UMR 5254, Université de Pau et des Pays de l'Adour, Hélioparc Pau Pyrénées, 2, av. P. Angot, 64053, Pau cedex 9, France.
Laboratoire de Chimie Analytique Bio-inorganique et Environnement, Institut Pluridisciplinaire de Recherche sur l'Environnement et les Matériaux, CNRS UMR 5254, Université de Pau et des Pays de l'Adour, Hélioparc Pau Pyrénées, 2, av. P. Angot, 64053, Pau cedex 9, France.
J Chromatogr A. 2014 May 2;1340:1-7. doi: 10.1016/j.chroma.2014.03.013. Epub 2014 Mar 11.
Large volume injection (LVI)-in port silylation coupled to gas chromatography-mass spectrometry (GC-MS) for the determination of alkylphenols (APs) in water samples applying four different extraction approaches was evaluated. Among the variables studied for in-port derivatization, vent time, cryo-focusing temperature and the ratio solvent volume/N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) volume were optimized using an experimental design approach. Regarding the extraction techniques, different approaches previously optimized in the research group were tested. On the one hand different polymeric materials were tested: silicon rod (SR), polyethersulfone (PES) and polydimethylsiloxane (PDMS), the latter in the stir-bar sorptive extraction format (SBSE-PDMS). PES was chosen among the polymeric materials due to the higher recoveries (compared with SR) and lower price (compared to PDMS in the stir-bar sorptive extraction, SBSE-PDMS). Both MASE and PES protocols were selected at this point for further method validation and application to real samples. Finally, the developed methods were validated and applied to the determination of target analytes in various aqueous environmental matrices, including estuarine water and wastewater. Acceptable repeatability in the case of MASE (5-17%) and PES (7-21%) procedures and method detection limits (MDLs, 5-123 and 28-328 ng L(-1) for PES and MASE, respectively) were obtained for most analytes. In terms of apparent recoveries in the presence of matrix, estuarine and effluent samples showed no significant matrix effect (apparent recoveries in the 73-121% for PES and 74-128% for MASE), while a stronger matrix effect was observed for influent wastewater samples (98-132% for PES and 65-156% for MASE). Both MASE and PES extractions combined with LVI-in-port derivatization-GC-MS were applied to the determination of APs in the estuary of Bilbao (Gulf of Biscay, Spain).
采用四种不同提取方法，评价了大体积进样（LVI）-进样硅烷化结合气相色谱-质谱（GC-MS）测定水样中烷基酚（APs）。在对进样衍生化进行研究的变量中，通过实验设计方法优化了通风时间、冷聚焦温度和溶剂体积/N,O-双（三甲基硅基）三氟乙酰胺（BSTFA）体积比。关于提取技术，测试了研究组先前优化的不同方法。一方面，测试了不同的聚合材料：硅棒（SR）、聚醚砜（PES）和聚二甲基硅氧烷（PDMS），后者采用搅拌棒吸附萃取格式（SBSE-PDMS）。由于回收效率较高（与 SR 相比）且价格较低（与搅拌棒吸附萃取中的 PDMS 相比，SBSE-PDMS），因此在聚合材料中选择了 PES。此时，选择 MASE 和 PES 方案进行进一步的方法验证，并应用于实际样品。最后，开发的方法进行了验证，并应用于各种水环境污染基质中目标分析物的测定，包括河口水和废水。MASE（5-17%）和 PES（7-21%）程序的可重复性和方法检测限（MDLs，对于大多数分析物，PES 和 MASE 的值分别为 5-123 和 28-328 ng L(-1)）均可接受。在基质存在的情况下，河口和废水样品的表观回收率没有明显的基质效应（PES 的回收率为 73-121%，MASE 的回收率为 74-128%），而进水废水样品的基质效应较强（PES 的回收率为 98-132%，MASE 的回收率为 65-156%）。MASE 和 PES 提取结合 LVI-进样衍生化-GC-MS 均应用于测定西班牙比斯开湾（毕尔巴鄂河口）的 APs。
