A fully automated analytical platform that seamlessly integrates online water sampling-sample preparation-gas chromatography-mass spectrometry (GC-MS) was developed for ultraviolet (UV) filters in this work. The online water sampling system consisted of a conventional sample vial (slightly modified to have both inlet and outlet ports), two tubings and a peristaltic pump, which controlled the water flow into and out of the vial. The sample preparation segment consists of miniscale liquid-liquid extraction (msLLE), coupled to full evaporation dynamic headspace concentration (FEDHS) on a commercial dual-arm autosampler. The extract from the msLLE step was subjected to a derivatization step, before being passed through a Tenax TA sorbent tube at the FEDHS stage. UV filters were used as model compounds in this work due to their potential endocrine and developmental toxicities, including benzhydrol, 2-ethylhexyl salicylate, homosalate, 2-hydroxy-4-methoxybenzophenone, 3-(4'-methylbenzylidene) camphor and benzophenone. The analytes (of which the first four underwent derivatization, by virtue of them possessing hydroxyl groups, but not the last two) were concentrated on the sorbent, and were thermally desorbed before being introduced to the GC-MS system for analysis. An orthogonal array design (OAD) strategy was employed to facilitate the optimization of the msLLE and derivatization factors while univariate optimization was performed for FEDHS. The optimized settings achieved low limits of detection (0.6-9.7 ng L-1) with good linearity (r2 ≥ 0.9926), and satisfactory absolute extraction recoveries (62.0%-80.7%) were obtained. The fully automated online water sampling-extraction/concentration-detection approach was demonstrated by applying it to the analysis of swimming pool water. Relative recoveries of the analytes in the pool water ranged from 85.4% to 118.2%. The described procedure has the potential to be a fully automated online water sampling-msLLE-FEDHS-GC-MS platform for the purpose of conducting routine onsite water analysis.

中文翻译：

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集水样-微型-液-液萃取-全蒸发动态顶空浓缩-气相色谱-质谱于一体的全自动分析平台，用于紫外滤光片的分析

在这项工作中，为紫外线 (UV) 过滤器开发了一个无缝集成在线水采样-样品制备-气相色谱-质谱 (GC-MS) 的全自动分析平台。在线水采样系统由一个传统的样品瓶（稍微修改为具有入口和出口端口）、两个管道和一个蠕动泵组成，该泵控制进出样品瓶的水流。样品制备部分包括微型液-液萃取 (msLLE)，与商用双臂自动进样器上的全蒸发动态顶空浓缩 (FEDHS) 相结合。来自 msLLE 步骤的提取物经过衍生化步骤，然后在 FEDHS 阶段通过 Tenax TA 吸附剂管。由于其潜在的内分泌和发育毒性，紫外线过滤剂被用作这项工作中的模型化合物，包括二苯甲醇、水杨酸 2-乙基己酯、高水杨酸酯、2-羟基-4-甲氧基二苯甲酮、3-(4'-甲基亚苄基) 樟脑和二苯甲酮。分析物（其中前四种经历衍生化，因为它们具有羟基，但不是最后两种）在吸附剂上浓缩，并在引入 GC-MS 系统进行分析之前进行热解吸。采用正交阵列设计 (OAD) 策略来促进 msLLE 和衍生因子的优化，同时对 FEDHS 进行单变量优化。优化设置实现了低检测限 (0.6-9.7 ng L-1)、良好的线性 (r2 ≥ 0.9926) 和令人满意的绝对提取回收率 (62. 0%-80.7%)。通过将其应用于游泳池水的分析，证明了全自动在线水采样-提取/浓度-检测方法。池水中分析物的相对回收率为 85.4% 至 118.2%。所描述的程序有可能成为一个全自动在线水采样-msLLE-FEDHS-GC-MS 平台，用于进行常规现场水分析。