PDF(Pubmed)
Abstract：
Identifying transformed emerging contaminants in complex environmental compartments is a challenging but meaningful task. Substituted para-phenylenediamine quinones (PPD-quinones) are emerging contaminants originating from rubber antioxidants and have been proven to be toxic to the aquatic species, especially salmonids. The emergence of multiple PPD-quinones in various environmental matrices and evidence of their specific hazards underscore the need to understand their environmental occurrences. Here, we introduce a fragmentation pattern-based nontargeted screening strategy combining full MS/All ion fragmentation/neutral loss-ddMS2 scans to identify potential unknown PPD-quinones in different environmental matrices. Using diagnostic fragments of m/z 170.0600, 139.0502, and characteristic neutral losses of 199.0633, 138.0429 Da, six known and three novel PPD-quinones were recognized in air particulates, surface soil, and tire tissue. Their specific structures were confirmed, and their environmental concentration and composition profiles were clarified with self-synthesized standards. N-(1-methylheptyl)-N\'-phenyl-1,4-benzenediamine quinone (8PPD-Q) and N,N\'-di(1,3-dimethylbutyl)-p-phenylenediamine quinone (66PD-Q) were identified and quantified for the first time, with their median concentrations found to be 0.02-0.21 μg·g-1 in tire tissue, 0.40-2.76 pg·m-3 in air particles, and 0.23-1.02 ng·g-1 in surface soil. This work provides new evidence for the presence of unknown PPD-quinones in the environment, showcasing a potential strategy for screening emerging transformed contaminants in the environment.
摘要：
在复杂的环境隔室中识别转化的新兴污染物是一项具有挑战性但有意义的任务。取代的对苯二胺醌（PPD-醌）是源自橡胶抗氧化剂的新兴污染物，已被证明对水生物种有毒，尤其是鲑鱼.多种PPD-醌在各种环境矩阵中的出现及其特定危害的证据突显了了解其环境发生的必要性。这里,我们引入了一种基于碎片模式的非靶向筛选策略，该策略结合了完整的MS/所有离子碎片/中性损失-ddMS2扫描，以识别不同环境基质中潜在的未知PPD-醌。使用m/z170.0600、139.0502的诊断片段和199.0633、138.0429Da的特征中性损失，在空气颗粒物中发现了六种已知的和三种新型的PPD-醌，表层土壤,和轮胎组织。它们的特定结构得到证实，并以自合成标准阐明了它们的环境浓度和组成概况。N-(1-甲基庚基)-N'-苯基-1,4-苯二胺醌(8PPD-Q)和N,首次对N-二(1,3-二甲基丁基)-对苯二胺醌(66PD-Q)进行鉴定和定量,轮胎组织中的中值浓度为0.02-0.21μg·g-1，空气颗粒中的0.40-2.76pg·m-3，表层土壤为0.23-1.02ng·g-1。这项工作为环境中存在未知的PPD-醌提供了新的证据，展示了筛选环境中新兴转化污染物的潜在策略。
