We assessed the oxidative potential (OP) of 135 individual polycyclic aromatic hydrocarbons (PAHs) using the dithiolthreitol (DTT) consumption assay. The OP of atmospheric fine particulate matter (PM2.5) has been linked to organic content, which includes PAHs. 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). We found that the PAHs ΔGrxn calculated from the DTT assay results match literature reduction potential values (r2 = 0.97), while DTT50 results had no correlations with the computed ΔGrxn values (r2 &lt; 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 several PAH subclasses, UPAH, HPAH, and OHPAH, 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 filter extracts were measured in the DTT assay, alongside mixtures of analytical standards prepared to match measured 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 picture of the complexity of OP in ambient PM2.5.

Combination of DTT assay results and thermodynamic calculations to assess the oxidative potential of PAHs in ambient PM2.5

ACS Fall 2021

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