The complexation of atmospheric Brown carbon surrogates on the generation of hydroxyl radical from transition metals in simulated lung fluid.

ABSTRACT

Atmospheric particulate matter (PM) poses great adverse effects through the production of reactive oxygen species (ROS). Various components in PM are acknowledged to induce ROS formation, while the interactions among chemicals remain to be elucidated. Here, we systematically investigate the influence of Brown carbon (BrC) surrogates (e.g., imidazoles, nitrocatechols and humic acid) on hydroxyl radical (OH) generation from transition metals (TMs) in simulated lung fluid. Present results show that BrC has an antagonism (interaction factor 20-90 %) with Cu2+ in OH generation upon the interaction with glutathione, in which the concentrations of BrC and TMs influence the extent of antagonism. Rapid OH generation in glutathione is observed for Fe2+, while OH formation is very little for Fe3+. The compositions of antioxidants (e.g., glutathione, ascorbate, urate), resembling the upper and lower respiratory tract, respond differently to BrC and TMs (Cu2+, Fe2+ and Fe3+) in OH generation and the degree of antagonism. The complexation equilibrium constants and site numbers between Cu2+ and humic acid were further analyzed using fluorescence quenching experiments. Possible complexation products among TMs, 4-nitrocatechol and glutathione were also identified using quadropule-time-of-flight mass spectrometry. The results suggest atmospheric BrC widely participate in complexation with TMs which influence OH formation in the human lung fluid, and complexation should be considered in evaluating ROS formation mediated by ambient PM.