Research Institute for Pesticides and Water, University Jaume I, 12071 Castellón, Spain.
J Chromatogr A. 2011 Jan 14;1218(2):303-15. doi: 10.1016/j.chroma.2010.11.010. Epub 2010 Nov 16.
In this work, a multiclass screening method for organic contaminants in natural and wastewater has been developed and validated for qualitative purposes, i.e. to ensure the reliable and sensitive identification of compounds detected in samples at a certain level of concentration. The screening is based on the use of GC-TOF MS, and the sample procedure involves solid phase extraction with C(18) cartridges. Around 150 organic contaminants from different chemical families were investigated, including PAHs, octyl/nonyl phenols, PCBs, PBDEs and a notable number of pesticides, such as insecticides (organochlorines, organophosphorus, carbamates and pyrethroids), herbicides (triazines and chloroacetanilides), fungicides and several relevant metabolites. Surface water, ground water and effluent wastewater were spiked with all target analytes at three concentration levels (0.02, 0.1 and 1 μg/L). Influent wastewater and raw leachate from a municipal solid waste treatment plant were spiked at two levels (0.1 and 1 μg/L). Up to five m/z ions were evaluated for every compound. The identification criterion was the presence of, at least, two m/z ions at the expected retention time, measured at their accurate mass, and the accomplishment of the Q/q(i) intensity ratio within specified tolerances. The vast majority of compounds investigated were correctly identified in the samples spiked at 1 μg/L. When analyte concentration was lowered down to 0.1 μg/L the identification was more problematic, especially in complex-matrix samples like influent wastewater. On the contrary, many contaminants could be properly identified at the lowest level 0.02 μg/L in cleaner matrices. The procedure was applied to the screening of water samples of different origin and matrix composition and allowed the detection of several target contaminants. A highly reliable identification could be carried out thanks to the sensitive full-spectrum acquisition at accurate mass, the high selectivity reached with the use of narrow-mass window extracted ion chromatograms, the low mass errors observed in the positive detections and the Q/q ratio accomplishment.
在这项工作中，开发并验证了一种用于天然水和废水的有机污染物多组分筛选方法，目的是确保在一定浓度水平下对样品中检测到的化合物进行可靠和灵敏的鉴定。筛选基于 GC-TOF MS 的使用，样品前处理方法包括 C(18)柱固相萃取。研究了来自不同化学家族的约 150 种有机污染物，包括多环芳烃、辛基/壬基酚、多氯联苯、PBDE 和相当数量的农药，如杀虫剂（有机氯、有机磷、氨基甲酸酯和拟除虫菊酯）、除草剂（三嗪类和氯乙酰胺类）、杀真菌剂和几种相关代谢物。地表水、地下水和废水均以三个浓度水平（0.02、0.1 和 1 μg/L）添加所有目标分析物。进水和城市固体废物处理厂的原始渗滤液以两个浓度水平（0.1 和 1 μg/L）添加。对每个化合物评估了多达五个 m/z 离子。鉴定标准是在准确质量下，在所测保留时间处至少存在两个 m/z 离子，并且在指定公差内完成 Q/q(i)强度比。在所添加浓度为 1 μg/L 的样品中，绝大多数被研究的化合物都能正确识别。当分析物浓度降低至 0.1 μg/L 时，鉴定就变得更加困难，特别是在像进水这样的复杂基质样品中。相反，在更清洁的基质中，许多污染物可以在最低浓度 0.02 μg/L 下正确识别。该程序已应用于不同来源和基质组成的水样筛选，并允许检测到几种目标污染物。由于在准确质量下进行了灵敏的全谱采集，使用窄质量窗口提取离子色谱图达到了高选择性，在正检测中观察到的质量误差低，以及 Q/q 比的完成，因此可以进行高度可靠的鉴定。
