多环芳烃(PAH)衍生物构成了一类重要的新兴污染物,已在各种环境基质中普遍检测到,有些甚至表现出比其相应的亲本PAHs更高的毒性。迄今为止,与亲本PAHs相比,较少的系统总结和再分析是可用于PAH衍生物与大的环境问题。这篇综述总结了目前关于化学物质的知识,levels,生物转化模式,化学分析方法,具有代表性生物标志物的内部暴露途径,和PAH衍生物的毒性,主要关注硝化多环芳烃(NPAHs),含氧多环芳烃(OPAHs),卤化多环芳烃(XPAHs),和烷基化PAHs(APAHs)。来自四个类别的188种化合物的集合,44NPAHs,36OPAHs,56APAHs,和52种XPAHs,已从114项研究中汇编,这些研究记录了PAH衍生物的环境存在。这些化合物表现出的加权平均空气浓度从0.019pg/m3的下限变化到4060pg/m3的较高阈值。利用全面的二维气相色谱与高分辨率飞行时间质谱(GC×GC-TOF-MS)的不同分析方法,气相色谱-飞行时间质谱联用(GC-TOF-MS),综合二维气相色谱-四极杆质谱联用(GC×GC-QQQ-MS),和傅里叶变换离子回旋共振质谱(FT-ICRMS),本文还对PAH衍生物鉴定所采用的非针对性策略进行了综述。此外,对每个类别的生物转化模式进行了深入分析,包括特定生物转化反应类型的可能性。对于毒性,我们主要总结了关键的代谢激活途径,这可能导致能够与DNA和组织蛋白共价结合的反应性代谢物的形成,和潜在的健康结果,如致癌性和遗传毒性,氧化应激,炎症和免疫毒性,以及可能由芳烃受体(AhR)介导的发育毒性。最后,我们指出了研究挑战,并强调需要进一步研究确定PAH衍生物,跟踪外部暴露水平,评估内部暴露水平和相关毒性,澄清暴露途径,并考虑混合暴露的影响。这篇综述旨在提供对PAH衍生物鉴定的广泛理解,环境发生,人体暴露,生物转化,和毒性,为指导该未开发地区的未来研究提供了有价值的参考。
Polycyclic aromatic hydrocarbon (PAH) derivatives constitute a significant class of emerging contaminants that have been ubiquitously detected in diverse environmental matrixes, with some even exhibiting higher toxicities than their corresponding parent PAHs. To date, compared with parent PAHs, fewer systematic summaries and reanalyses are available for PAH derivatives with great environmental concerns. This review summarizes the current knowledge on the chemical species, levels, biotransformation patterns, chemical analytical methods, internal exposure routes with representative biomarkers, and toxicity of PAH derivatives, primarily focusing on nitrated PAHs (NPAHs), oxygenated PAHs (OPAHs), halogenated PAHs (XPAHs), and alkylated PAHs (APAHs). A collection of 188 compounds from four categories, 44 NPAHs, 36 OPAHs, 56 APAHs, and 52 XPAHs, has been compiled from 114 studies that documented the environmental presence of PAH derivatives. These compounds exhibited weighted average air concentrations that varied from a lower limit of 0.019 pg/m3 to a higher threshold of 4060 pg/m3. Different analytical methods utilizing comprehensive two-dimensional gas chromatography coupled with high-resolution time-of-flight mass spectrometry (GC × GC-TOF-MS), gas chromatography coupled to time-of-flight mass spectrometry (GC-TOF-MS), comprehensive two-dimensional gas chromatography coupled to quadrupole mass spectrometry (GC × GC-QQQ-MS), and Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS), that adopted untargeted strategies for the identification of PAH derivatives are also reviewed here. Additionally, an in-depth analysis of biotransformation patterns for each category is provided, including the likelihood of specific biotransformation reaction types. For the toxicity, we primarily summarized key metabolic activation pathways, which could result in the formation of reactive metabolites capable of covalently bonding with DNA and tissue proteins, and potential health outcomes such as carcinogenicity and genotoxicity, oxidative stress, inflammation and immunotoxicity, and developmental toxicity that might be mediated by the aryl hydrocarbon receptor (AhR). Finally, we pinpoint research challenges and emphasize the need for further studies on identifying PAH derivatives, tracking external exposure levels, evaluating internal exposure levels and associated toxicity, clarifying exposure routes, and considering mixture exposure effects. This review aims to provide a broad understanding of PAH derivatives\' identification, environmental occurrence, human exposure, biotransformation, and toxicity, offering a valuable reference for guiding future research in this underexplored area.