Department of Civil and Environmental Engineering, University of Illinois at Urbana-Champaign , 205 North Mathews Avenue, Urbana, Illinois 61801, United States.
Department of Chemistry, University of Illinois at Urbana-Champaign , 505 S. Mathews Avenue, Urbana, Illinois 61801, United States.
Environ Sci Technol. 2018 Feb 20;52(4):2261-2270. doi: 10.1021/acs.est.7b04261. Epub 2018 Jan 31.
We assessed the interactions among the particulate matter (PM) components in generating the reactive oxygen species (ROS) based on a dithiothreitol (DTT) assay. We started with the standard solutions of known redox-active substances, i.e., quinones (9,10-phenanthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, and 5-hydroxy-1,4-naphthoquinone) and metals [Fe (II), Mn (II), and Cu (II)]. Both DTT consumption and hydroxyl radical (·OH) generation were measured in the DTT assay. The interactions of Fe were additive with quinones in DTT consumption but strongly synergistic in ·OH generation. Cu showed antagonistic interactions with quinones in both DTT consumption and ·OH generation. Mn interacted synergistically with quinones in DTT oxidation but antagonistically in ·OH generation. The nature of the interactions of these metals (Fe, Mn, and Cu) with ambient humic-like substances (HULIS) resembled that with quinones, although the intensity of interactions were weaker in DTT consumption than ·OH generation. Finally, we demonstrated that the DTT consumption capability of ambient PM can be well explained by HULIS, three transition metals (Fe, Mn, and Cu), and their interactions, but ·OH generation involves a contribution (∼50%) from additional compounds (aliphatic species or metals other than Fe, Mn, and Cu) present in the hydrophilic PM fraction. The study highlights the need to account for the interactions between organic compounds and metals, while apportioning the relative contributions of chemical components in the PM oxidative potential.
我们基于二硫苏糖醇(DTT)测定法评估了颗粒物(PM)成分在生成活性氧(ROS)方面的相互作用。我们从已知氧化还原活性物质的标准溶液开始,即醌类(9,10-菲醌、1,2-萘醌、1,4-萘醌和 5-羟基-1,4-萘醌)和金属[Fe(II)、Mn(II)和 Cu(II)]。在 DTT 测定中均测量 DTT 消耗和羟基自由基(·OH)生成。Fe 在 DTT 消耗中与醌类呈相加作用,但在·OH 生成中呈强烈协同作用。Cu 在 DTT 消耗和·OH 生成中与醌类均呈拮抗作用。Mn 在 DTT 氧化中与醌类呈协同作用,但在·OH 生成中呈拮抗作用。这些金属(Fe、Mn 和 Cu)与环境类腐殖质物质(HULIS)的相互作用性质与醌类相似,尽管在 DTT 消耗中相互作用的强度比·OH 生成中弱。最后,我们证明环境 PM 的 DTT 消耗能力可以很好地由 HULIS、三种过渡金属(Fe、Mn 和 Cu)及其相互作用来解释,但·OH 生成涉及亲水性 PM 分馏中存在的其他化合物(脂肪族物质或除 Fe、Mn 和 Cu 以外的金属)的贡献(约 50%)。该研究强调了需要考虑有机化合物和金属之间的相互作用,同时分配 PM 氧化潜力中化学组分的相对贡献。