Köppe Toni, Jewell Kevin S, Ehlig Björn, Wick Arne, Koschorreck Jan, Ternes Thomas A
Federal Institute of Hydrology, Am Mainzer Tor 1, 56068 Koblenz, Germany.
Federal Environment Agency (Umweltbundesamt), Colditzstraße 34, 14193, Berlin, Germany.
Water Res. 2023 Feb 1;229:119304. doi: 10.1016/j.watres.2022.119304. Epub 2022 Oct 28.
Non-target screening of suspended particulate matter (SPM), collected from the German rivers Rhine and Saar, was conducted with the goal of identifying organic, permanent cationic contaminants and of estimating their temporal trends over an extended period. Therefore, annual composite samples of SPM, provided by the German Environmental Specimen Bank, were extracted and analyzed with high resolution LC-QToF-MS/MS. To facilitate the identification of substances belonging to the class "permanent cations", prioritization methods were applied utilizing the physicochemical properties of these compounds. These methods include both interactions of the analyte molecules with cation exchange resins and analyzing mass deviations when changing from non-deuterated to deuterated mobile phase solvents during LC-MS analysis. By applying both methods in a combined approach, 123 of the initially detected 2695 features were prioritized, corresponding to a 95% data reduction. This led to the identification of 22 permanent cationic species. The organic dyes Basic Yellow 28 and Fluorescent Brightener 363 as well as two quaternary ammonium compounds (QACs) were detected in environmental samples for the first time to best of or knowledge. The other compounds include additional QACs, as well as quaternary tri-phenylphosphonium compounds (QPC/TPP). In addition to identification, we determined temporal trends of all compounds over a period of 13 years and assessed their ecotoxicological relevance based on estimated concentrations. The two QACs oleyltrimethylammonium and eicosyltrimethylammonium show significant increasing trends in the Rhine SPM and maximum concentrations in the Saar SPM of about 900 and 1400 µg/kg, respectively. In the case of the dyes, constant trends have been observed at the end of the studied period, but also maximum concentrations of 400 µg/kg for Basic Yellow 28 in 2006 and 1000 µg/kg for Fluorescent Brightener 363 in 2015, potentially indicating a strong ecotoxicological risk.
对从德国莱茵河和萨尔河采集的悬浮颗粒物（SPM）进行非目标筛查，目的是识别有机、永久性阳离子污染物，并评估其在较长时期内的时间趋势。因此，提取了由德国环境样本库提供的SPM年度混合样本，并采用高分辨率液相色谱-四极杆飞行时间串联质谱（LC-QToF-MS/MS）进行分析。为便于识别属于“永久性阳离子”类别的物质，利用这些化合物的物理化学性质应用了优先排序方法。这些方法包括分析物分子与阳离子交换树脂的相互作用，以及在液相色谱-质谱分析中从不氘代流动相溶剂变为氘代流动相溶剂时分析质量偏差。通过将两种方法结合使用，对最初检测到的2695个特征中的123个进行了优先排序，相当于数据量减少了95%。这导致识别出22种永久性阳离子物质。据我们所知，环境样本中首次检测到有机染料碱性黄28和荧光增白剂363以及两种季铵化合物（QACs）。其他化合物包括额外的QACs以及季三苯基鏻化合物（QPC/TPP）。除了识别之外，我们还确定了所有化合物在13年期间的时间趋势，并根据估计浓度评估了它们的生态毒理学相关性。两种QACs油基三甲基铵和二十烷基三甲基铵在莱茵河SPM中呈现出显著的上升趋势，在萨尔河SPM中的最大浓度分别约为900和1400μg/kg。对于染料，在研究期结束时观察到趋势稳定，但碱性黄28在2006年的最大浓度为400μg/kg，荧光增白剂363在2015年的最大浓度为1000μg/kg，这可能表明存在很强的生态毒理学风险。
