Department of Analytical Chemistry, University of the Basque Country (UPV/EHU), Leioa, Basque Country 48940, Spain; Research Centre for Experimental Marine Biology and Biotechnology, University of the Basque Country (UPV/EHU), Plentzia, Basque Country 48620, Spain.
Department of Analytical Chemistry, University of the Basque Country (UPV/EHU), Leioa, Basque Country 48940, Spain.
J Chromatogr A. 2023 Aug 30;1705:464141. doi: 10.1016/j.chroma.2023.464141. Epub 2023 Jun 16.
In this work, a comprehensive method for the simultaneous determination of 33 diverse persistent and mobile organic compounds (PMOCs) in human urine was developed by dilute-and-shoot (DS) followed by mixed-mode liquid chromatography coupled with tandem mass spectrometry (MMLC-MS/MS). In the sample preparation step, DS was chosen since it allowed the quantification of all targets in comparison to lyophilization. For the chromatographic separation, Acclaim Trinity P1 and P2 trimodal columns provided greater capacity for retaining PMOCs than reverse phase and hydrophilic interaction liquid chromatography. Therefore, DS was validated at 5 and 50 ng/mL in urine with both mixed mode columns at pH = 3 and 7. Regarding figures of merit, linear calibration curves (r > 0.999) built between instrumental quantification limits (mostly below 5 ng/mL) and 500 ng/mL were achieved. Despite only 60% of the targets were recovered at 5 ng/mL because of the dilution, all PMOCs were quantified at 50 ng/mL. Using surrogate correction, apparent recoveries in the 70-130% range were obtained for 91% of the targets. To analyse human urine samples, the Acclaim Trinity P1 column at pH = 3 and 7 was selected as a consensus between analytical coverage (i.e. 94% of the targets) and chromatographic runs. In a pooled urine sample, industrial chemicals (acrylamide and bisphenol S), biocides and their metabolites (2-methyl-4-isothiazolin-3-one, dimethyl phosphate, 6-chloropyridine-3-carboxylic acid, and ammonium glufosinate) and an artificial sweetener (aspartame) were determined at ng/mL levels. The outcomes of this work showed that humans are also exposed to PMOCs due to their persistence and mobility, and therefore, further human risk assessment is needed.
在这项工作中，通过稀释-进样（DS） followed by 混合模式液相色谱串联质谱法（MMLC-MS/MS）开发了一种综合方法，用于同时测定人尿中 33 种不同的持久性和移动性有机化合物（PMOCs）。在样品制备步骤中，选择 DS 是因为它允许与冻干相比定量所有目标。对于色谱分离，Acclaim Trinity P1 和 P2 三模态柱比反相和亲水相互作用液相色谱具有更大的保留 PMOCs 的能力。因此，在 pH = 3 和 7 时，在两种混合模式柱上，在尿液中以 5 和 50 ng/mL 对 DS 进行了验证。关于衡量标准，在仪器定量限（大多低于 5 ng/mL）和 500 ng/mL 之间建立了线性校准曲线（r>0.999）。尽管由于稀释，只有 60%的目标在 5 ng/mL 时得到回收，但所有 PMOCs 都在 50 ng/mL 时定量。使用替代物校正，91%的目标获得了 70-130%范围内的表观回收率。为了分析人尿样，选择 Acclaim Trinity P1 柱在 pH = 3 和 7 作为分析覆盖率（即 94%的目标）和色谱运行之间的共识。在混合尿样中，以 ng/mL 水平测定了工业化学品（丙烯酰胺和双酚 S）、杀生物剂及其代谢物（2-甲基-4-异噻唑啉-3-酮、磷酸二甲酯、6-氯吡啶-3-羧酸和氨甲基膦酸）和一种人工甜味剂（阿斯巴甜）。这项工作的结果表明，由于其持久性和移动性，人类也会接触到 PMOCs，因此需要进一步进行人类风险评估。
