Screening p -Phenylenediamine Antioxidants, Their Transformation Products, and Industrial Chemical Additives in Crumb Rubber and Elastomeric Consumer Products
Screening p -Phenylenediamine Antioxidants, Their Transformation Products, and Industrial Chemical Additives in Crumb Rubber and Elastomeric Consumer Products
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筛选粒状橡胶和弹性消费品中的对苯二胺抗氧化剂、其转化产物以及工业化学添加剂
DOI：
10.1021/acs.est.2c07014
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发表时间：
2023
影响因子：
11.4
通讯作者：
Tian, Zhenyu
中科院分区：
文献类型：
--
作者：
Zhao, Haoqi Nina;Hu, Ximin;Gonzalez, Melissa;Rideout, Craig A.;Hobby, Grant C.;Fisher, Matthew F.;McCormick, Carter J.;Dodd, Michael C.;Kim, Kelly E.;Tian, Zhenyu
最近，由于剧毒的6PPD-醌，N,N'-取代的对苯二胺（PPD）抗氧化剂及其转化产物（TP）的道路释放受到了广泛关注。然而，再生轮胎橡胶产品中 PPD 和 TP 的出现情况仍不明确。在这里，我们使用液相色谱-串联质谱法分析了轮胎磨损颗粒 (TWP)、再生橡胶门垫和草坪碎胶中的七种 PPD 抗氧化剂、五种 PPD 醌 (PPDQ) 和其他五种 6PPD TP。所有样品中均存在 PPD 抗氧化剂、PPDQ 和其他 TP，其化学特征以 6PPD、DTPD、DPPD 及其相应的 PPDQ 为主。有趣的是，随着 PPD 衍生化学物质总浓度的降低，单个 [PPDQ]/[PPD] 和 [TP]/[PPD] 比率显着增加，表明随着环境风化的增加，TP（包括 PPDQ）在 PPD 衍生化合物中占主导地位。此外，我们还对 15 种其他工业橡胶添加剂（包括粘合剂、硫化促进剂、苯并三唑和苯并噻唑衍生物以及二苯胺抗氧化剂）进行了定量，观察到 PPD 衍生的化学浓度比这些经常研究的添加剂高 0.5-6 倍。我们还筛选了各种其他弹性消费品，持续检测实验室塞、运动鞋鞋底和橡胶花园软管样品中的 PPD 衍生化合物。这些数据强调，PPD 抗氧化剂、PPDQ 和相关 TP 是轮胎橡胶和弹性消费产品中以前被忽视的重要污染物类别。
Recently, roadway releases ofN,N′-substitutedp-phenylenediamine (PPD) antioxidants and their transformation products (TPs) received significant attention due to the highly toxic 6PPD-quinone. However, the occurrence of PPDs and TPs in recycled tire rubber products remains uncharacterized. Here, we analyzed tire wear particles (TWPs), recycled rubber doormats, and turf-field crumb rubbers for seven PPD antioxidants, five PPD-quinones (PPDQs), and five other 6PPD TPs using liquid chromatography-tandem mass spectrometry. PPD antioxidants, PPDQs, and other TPs were present in all samples with chemical profiles dominated by 6PPD, DTPD, DPPD, and their corresponding PPDQs. Interestingly, the individual [PPDQ]/[PPD] and [TP]/[PPD] ratios significantly increased as total concentrations of the PPD-derived chemical decreased, indicating that TPs (including PPDQs) dominated the PPD-derived compounds with increased environmental weathering. Furthermore, we quantified 15 other industrial rubber additives (including bonding agents, vulcanization accelerators, benzotriazole and benzothiazole derivatives, and diphenylamine antioxidants), observing that PPD-derived chemical concentrations were 0.5–6 times higher than these often-studied additives. We also screened various other elastomeric consumer products, consistently detecting PPD-derived compounds in lab stoppers, sneaker soles, and rubber garden hose samples. These data emphasize that PPD antioxidants, PPDQs, and related TPs are important, previously overlooked contaminant classes in tire rubbers and elastomeric consumer products.