Abstract Stir bar sorptive extraction (SBSE) has been developed in 1999 to efficiently extract and preconcentrate volatile compounds, and many applications have been found after that. This technique conforms to the principles of green chemistry. Here, we used an autosampler with an online thermal desorption unit connected to CGC-MS to analyze pesticides. This study describes the development of a highly sensitive extraction method based on SBSE for simultaneous determination of ultra-trace amounts of four pesticides λ-cyhalothrin, α-cypermethrin, tefluthrin, and dimefluthrin in environmental water samples. This method was compared to the standard liquid–liquid extraction. In this study, a totally solventless SBSE was applied to river and tap water samples for the extraction and preconcentration of four pesticides. PDMS-coated SBSEs of 10 mm × 1 mm thickness were used for this purpose, and SBSEs were directly placed into a large-volume injector of a CGC-MS for thermal desorption of the analytes. In all extractions, deltamethrin was used as an internal standard. This method showed linearity in the range of 1.0–200.0 ng L−1 for cyhalothrin, tefluthrin, and dimefluthrin and 10.0–800 ng L−1 for cypermethrin. Preconcentration factors of 179, 7, 162, and 166 were obtained with very low limits of detection of 0.32, 3.41, 0.36m and 0.69 ng L−1 for cyhalothrin, cypermethrin, tefluthrinm and dimefluthrin, respectively. These detection limits are thousands of times lower than that of the standard method of liquid–liquid extraction. Reproducibility of the method, based on the relative standard deviation, was better than 7.5% and recoveries for spiked tap and river water samples was within the range of 87.83–114.45%. The application of PDMS-coated SBSE coupled with CGC-MS equipped with a large volume injector thermal desorption unit can be used for ultra-trace analysis of environmental water samples. Solventless SBSE offers several advantages over conventional traditional liquid–liquid extraction such as being very fast and economical and provides better extraction without requiring any solvents; so it can be considered as a green method for the analysis of pesticides. Graphical abstract

中文翻译：

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开发用于超痕量测定河流和自来水样品中拟除虫菊酯类农药的无溶剂搅拌棒吸附萃取/热解吸大体积进样毛细管气相色谱-质谱法

摘要 搅拌棒吸附萃取 (SBSE) 于 1999 年开发，用于高效萃取和预浓缩挥发性化合物，此后发现了许多应用。该技术符合绿色化学的原理。在这里，我们使用带有连接到 CGC-MS 的在线热解吸装置的自动进样器来分析农药。本研究介绍了基于 SBSE 的高灵敏度提取方法的开发，用于同时测定环境水样中四种农药 λ-三氯氟氰菊酯、α-氯氰菊酯、七氟菊酯和二甲氟菊酯的超痕量。将该方法与标准液-液萃取进行了比较。在本研究中，将完全无溶剂的 SBSE 应用于河流和自来水样品，以提取和预浓缩四种农药。为此使用了 10 mm × 1 mm 厚的 PDMS 涂层 SBSE，并将 SBSE 直接放入 CGC-MS 的大容量进样器中，以对分析物进行热解吸。在所有提取中，溴氰菊酯用作内标。该方法显示出三氯氟氰菊酯、七氟菊酯和二甲氟菊酯在 1.0-200.0 ng L-1 范围内的线性，对于氯氰菊酯在 10.0-800 ng L-1 范围内线性。获得了 179、7、162 和 166 的预浓缩因子，三氟氯氰菊酯、氯氰菊酯、七氟菊酯和二甲氟菊酯的检测限分别为 0.32、3.41、0.36m 和 0.69 ng L-1，检测限非常低。这些检测限比标准液-液萃取方法低数千倍。基于相对标准偏差，该方法的重现性优于 7。5%，加标自来水和河水样品的回收率在 87.83-114.45% 的范围内。PDMS 涂层SBSE 与配备大容量进样器热脱附装置的CGC-MS 的应用可用于环境水样的超痕量分析。与传统的传统液-液萃取相比，无溶剂 SBSE 具有多项优势，例如非常快速且经济，并且无需任何溶剂即可提供更好的萃取效果；因此它可以被认为是一种分析农药的绿色方法。图形概要 与传统的传统液-液萃取相比，无溶剂 SBSE 具有多项优势，例如非常快速且经济，并且无需任何溶剂即可提供更好的萃取效果；因此它可以被认为是一种分析农药的绿色方法。图形概要 与传统的传统液-液萃取相比，无溶剂 SBSE 具有多项优势，例如非常快速且经济，并且无需任何溶剂即可提供更好的萃取效果；因此它可以被认为是一种分析农药的绿色方法。图形概要