The oxidative potential (OP) of atmospheric fine particulate matter (PM2.5) has been linked to organic content, which includes polycyclic aromatic hydrocarbons (PAHs). The OP of 135 individual PAHs (including six subclasses) was measured using the dithiolthreitol (DTT) consumption assay. The DTT assay results were used to compute the concentration of each PAH needed to consume 50% of the DTT concentration in the assay (DTT50), and the reduction potential of the PAHs (ΔGrxn). Computed reduction potential results were found to match literature reduction potential values (r2 = 0.97), while DTT50 results had no correlations with the computed ΔGrxn values (r2 < 0.1). The GINI equality index was used to assess the electron distribution across the surface of unreacted and reacted PAHs. GINI values correlated with ΔGrxn in UPAH, HPAH, and OHPAH subclasses, as well as with all 135 PAHs in this study but did not correlate with DTT50, indicating that electron dispersion is linked to thermodynamic reactions and structural differences in PAHs, but not linked to the OP of PAHs. Three ambient PM2.5 filters extracts were measured in the DTT assay, alongside mixtures of analytical standards prepared to match PAH concentrations in the filter extracts to test if the OP follows an additive model of toxicity. The additive prediction model did not accurately predict the DTT consumption in the assay for any of the prepared standard mixtures or ambient PM2.5 filter extracts, indicating a much more complex model of toxicity for the OP of PAHs in ambient PM2.5. This study combined computed molecular properties with toxicologically relevant assay results to probe the OP of anthropogenically driven portions of ambient PM2.5, and results in a better understanding of the complexity of ambient PM2.5 OP.
Keywords: Dithiothreitol (DTT); Oxidative potential; Polycyclic aromatic hydrocarbons (PAHs).
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