Assessment of Interactions between Transition Metals and Atmospheric Organics: Ascorbic Acid Depletion and Hydroxyl Radical Formation in Organic-Metal Mixtures

Excessive oxidative stress has been recognized as an important cause of the adverse health effects associated with exposure to ambient particulate matter (PM). Transition metals (TMs) (e.g., iron (Fe) and copper (Cu)) are known catalysts in the formation of reactive oxygen species (ROS) in surrogate lung fluid containing antioxidants. Humic-like substances (HULIS), extracted from atmospheric aerosols, retain the compositional complexity of real-world samples. It contains mixtures of organics that chelate TMs and was used in this work to examine the roles of atmospheric organics in affecting ROS formation and antioxidant depletion by TMs. Two types of metal-binding organics known to be present in HULIS, oxygen-containing (i.e., carboxylic acids) and reduced-nitrogen-containing organics (i.e., imidazoles), were first investigated for their effects on the ascorbic acid depletion (denoted as OPAA) and hydroxyl radical formation (denoted as OP•OH) from both Fe(II) and Cu(II) in phosphate buffered saline (pH 7.40) containing ascorbic acid. Our results show that carboxylic acids enhance the OPAA and OP•OH by TMs while imidazoles suppress them. Similar experiments using three HULIS samples with distinctly different chemical compositions revealed complexity in metal-organics interactions. While ambient HULIS showed negligible impacts, two biomass burning source HULIS samples from rice straw and sugar cane leaf burning displayed unambiguous suppression or enhancement effects on OPAA and OP•OH by TMs. The effect was metal-specific and source HULIS-specific. The distinct behaviors of the three HULIS types can be explained by their different chemical compositions, for example, outstanding higher level of alkaloid compounds (e.g., imidazoles) in rice straw burning HULIS was consistent with the suppression effect exerted by this source of HULIS. In addition, we found OPAA and OP•OH are well-correlated while the proportion of OP•OH/OPAA by Cu is noticeably lower than that by Fe, indicating varying sensitivity of the metals to different OP end points. Our work highlights the importance and complexity of metal-organics interactions and the advantages of comeasurements of ROS generation and antioxidant depletion when assessing oxidative stress elicited by atmospheric PM.