N,N′-disubstituted -phenylenediamine-quinones (PPDQs) are oxidization derivatives of -phenylenediamines (PPDs) and have raised extensive concerns recently, due to their toxicities and prevalence in the environment, particularly in water environment. PPDQs are derived from tire rubbers, in which other PPD oxidization products besides reported PPDQs may also exist, e.g., unknown PPDQs and PPD-phenols (PPDPs). This study implemented nontarget analysis and profiling for PPDQ/Ps in aged tire rubbers using liquid chromatography-high-resolution mass spectrometry and a species-specific algorithm. The algorithm took into account the ionization behaviors of PPDQ/Ps in both positive and negative electrospray ionization, and their specific carbon isotopologue distributions. A total of 47 formulas of PPDQ/Ps were found and elucidated with tentative or accurate structures, including 25 PPDQs, 18 PPDPs and 4 PPD-hydroxy-quinones (PPDHQs). The semiquantified total concentrations of PPDQ/Ps were 14.08–30.62 μg/g, and the concentrations followed the order as: PPDPs (6.48–17.39) > PPDQs (5.86–12.14) > PPDHQs (0.16–1.35 μg/g). The high concentrations and potential toxicities indicate that these PPDQ/Ps could seriously threaten the eco-environment, as they may finally enter the environment, accordingly requiring further investigation. The analysis strategy and data-processing algorithm can be extended to nontarget analysis for other zwitterionic pollutants, and the analysis results provide new understandings on the environmental occurrence of PPDQ/Ps from source and overall perspectives.

中文翻译：

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通过 LC-HRMS 和特定化学物质算法对轮胎橡胶中的对苯二胺醌和苯酚进行非目标分析和表征


N,N'-二取代对苯二胺醌（PPDQ）是对苯二胺（PPD）的氧化衍生物，由于其毒性和在环境特别是水环境中的普遍存在，近年来引起了广泛的关注。 PPDQ源自轮胎橡胶，其中除了已报道的PPDQ之外还可能存在其他PPD氧化产物，例如未知的PPDQ和PPD-苯酚(PPDP)。本研究使用液相色谱-高分辨率质谱和物种特异性算法对老化轮胎橡胶中的 PPDQ/P 进行非目标分析和分析。该算法考虑了 PPDQ/Ps 在正电喷雾电离和负电喷雾电离中的电离行为及其特定的碳同位素分布。共发现并阐明了47个具有初步或准确结构的PPDQ/Ps分子式，其中包括25个PPDQs、18个PPDPs和4个PPD-羟基醌(PPDHQs)。 PPDQ/Ps 的半定量总浓度为 14.08–30.62 μg/g，浓度顺序为：PPDPs (6.48–17.39)> PPDQs (5.86–12.14)> PPDHQs (0.16–1.35 μg/g)。高浓度和潜在毒性表明这些PPDQ/Ps可能会严重威胁生态环境，因为它们最终可能进入环境，因此需要进一步调查。该分析策略和数据处理算法可推广到其他两性离子污染物的非目标分析，分析结果从源头和整体角度为PPDQ/Ps的环境发生提供了新的认识。