Transition metals and chemical compositions determine the oxidation capacity of atmospheric particulate matters

The knowledge of the causal relationship between exposure to airborne particulate matter (PM) and respiratory-related health issues remains unsatisfactory, owing to the complexities of physical and chemical characteristics in PM. One measure that greatly lifts the complexity is oxidative potential (OP), the overall production capacity of reactive oxygen species. We analyzed PM at different size fractions from three localities, exhibiting different source emission properties and photochemical aging states. We also investigated possible causes for their OPs, which were assessed using cellular and acellular assays. We found that higher PM mass did not always yield higher OP. Instead, chemical composition, modified by photochemical alteration (particle oxidation), played a critical role in the PM's reactivity. From a pollution hot spot to a downwind country town, the PM_2.5 levels (mean ± SD) were 9.3 ± 4.5, 9.7 ± 4.9, and 6.6 ± 4.7 microg/m³, respectively. In contrast, the PM mass-normalized OP values in the downwind region were approximately 20 % higher than those in the upwind region based on the cellular assay and about three times higher from the acellular assay. Enhanced PM OP is associated with atmospheric oxidation, approximated by sulfur and nitrogen oxidation ratios. We further identified transition metals, particularly copper, a single most important species group, the primary determinant to the values of OP measured, contributing directly to OP and indirectly through metal-oxides enhanced photochemical alterations to PM.