University of A Coruña, Grupo Química Analítica Aplicada (QANAP), University Institute of Research in Environmental Studies (IUMA), Department of Chemistry, Faculty of Sciences, Campus de A Coruña, s/n. 15071, A Coruña, Spain.
University of A Coruña, Grupo Química Analítica Aplicada (QANAP), University Institute of Research in Environmental Studies (IUMA), Department of Chemistry, Faculty of Sciences, Campus de A Coruña, s/n. 15071, A Coruña, Spain.
Anal Chim Acta. 2023 Nov 1;1280:341862. doi: 10.1016/j.aca.2023.341862. Epub 2023 Sep 30.
In recent decades, there has been a growing interest within the scientific community regarding the study of the fraction that could be released in simulated biological fluids to estimate in vitro bioaccessibility and bioavailability of compounds. Concerning particulate matter (PM), studies were essentially focused on metal (oid)s probably due to more complex methodologies needed for organic compounds, requiring extraction and pre-concentration steps from simulated fluids, followed by chromatographic analysis. Thus, the development of a simple and sensitive methodology for the analysis of multi-class organic compounds released in different inhalation simulated fluids would represent a great contribution to the field.
In this work, a methodology for the analysis of 49 organic pollutants, including 18 polycyclic aromatic hydrocarbons (PAHs), 12 phthalate esters (PAEs), 11 organophosphorus flame retardants (OPFRs), 6 synthetic musk compounds (SMCs) and 2 bisphenols released in simulated fluids from PM samples was developed. After a physiologically based extraction test (PBET) by using artificial lysosomal fluid (ALF) and a simulated body fluid (SBF, filling a dialysis membrane) to obtain in vitro inhalation bioaccessible and bioavailable fractions, respectively; compounds were determined by a vortex-assisted liquid-liquid extraction (VALLE) and a subsequent analysis by programmed temperature vaporization-gas chromatography-tandem mass spectrometry (PTV-GC-MS/MS). Experimental conditions concerning VALLE extraction (extraction time and amount of NaCl (g)) were optimized by using a central composite design (CCD), best MS/MS transitions were selected and matrix-matched calibration combined with use of labelled subrogate standards provided high sensitivity, minimization of matrix effects and recovering losses compensation.
The successful validation results obtained for most of the compounds demonstrated the effectiveness of the proposed methodology for the analysis of multi-class organic pollutants released in ALF and SBF for inhalation bioaccessibility and bioavailability assessment, respectively. Furthermore, applicability of the method was proved by analysing 20 p.m. samples, being the proposed in vitro PBET dialyzability approach for assessing organic pollutant's inhalation bioavailability applied to PM samples for the first time.
近几十年来，科学界越来越关注研究可在模拟生物流体中释放的部分，以估计化合物的体外生物可及性和生物利用度。对于颗粒物（PM），研究主要集中在金属（类）上，这可能是因为对于有机化合物，需要从模拟流体中进行提取和预浓缩步骤，然后进行色谱分析，因此，开发一种简单灵敏的分析方法对于多类有机化合物在不同吸入模拟液中释放具有重要意义。
本工作建立了一种分析 49 种有机污染物的方法，包括 18 种多环芳烃（PAHs）、12 种邻苯二甲酸酯（PAEs）、11 种有机磷阻燃剂（OPFRs）、6 种合成麝香化合物（SMCs）和 2 种双酚在 PM 样品模拟液中释放。在使用人工溶酶体液（ALF）和模拟体液（SBF，填充透析膜）进行基于生理的提取试验（PBET）后，分别获得体外吸入可及和可利用的分数；然后通过涡旋辅助液液萃取（VALLE）和随后的程序升温汽化-气相色谱-串联质谱（PTV-GC-MS/MS）分析来确定化合物。通过使用中心组合设计（CCD）优化了 VALLE 萃取（萃取时间和 NaCl（g）量）的实验条件，选择了最佳的 MS/MS 跃迁，并使用标记替代标准进行基质匹配校准，从而提供了高灵敏度、最小化基质效应和恢复损失补偿。
大多数化合物的成功验证结果表明，该方法对于分析 ALF 和 SBF 中释放的多类有机污染物用于吸入生物可及性和生物利用度评估是有效的。此外，通过分析 20μm 样品证明了该方法的适用性，这是首次将该体外 PBET 可透析性方法应用于 PM 样品评估有机污染物的吸入生物利用度。
