Abstract. Particulate matter (PM), of which a significant fraction is comprised of secondary organic aerosols (SOA), has received considerable attention due to its health implications. In this study, the water-soluble oxidative potential (OPWS) of SOA generated from the photooxidation of biogenic and anthropogenic hydrocarbon precursors (isoprene, α-pinene, β-caryophyllene, pentadecane, m-xylene, and naphthalene) under different reaction conditions (RO2+ HO2 vs. RO2+ NO dominant, dry vs. humid) was characterized using dithiothreitol (DTT) consumption. The measured intrinsic OPWS-DTT values ranged from 9 to 205 pmol min−1 µg−1 and were highly dependent on the specific hydrocarbon precursor, with naphthalene and isoprene SOA generating the highest and lowest OPWS-DTT values, respectively. Humidity and RO2 fate affected OPWS-DTT in a hydrocarbon-specific manner, with naphthalene SOA exhibiting the most pronounced effects, likely due to the formation of nitroaromatics. Together, these results suggest that precursor identity may be more influential than reaction condition in determining SOA oxidative potential, demonstrating the importance of sources, such as incomplete combustion, to aerosol toxicity. In the context of other PM sources, all SOA systems, with the exception of naphthalene SOA, were less DTT active than ambient sources related to incomplete combustion, including diesel and gasoline combustion as well as biomass burning. Finally, naphthalene SOA was as DTT active as biomass burning aerosol, which was found to be the most DTT-active OA source in a previous ambient study. These results highlight a need to consider SOA contributions (particularly from anthropogenic hydrocarbons) to health effects in the context of hydrocarbon emissions, SOA yields, and other PM sources.

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Abstract. An automated analytical system was developed for measuring the oxidative potential (OP) with the dithiothreitol (DTT) assay of filter extracts that include both watersoluble and water-insoluble (solid) aerosol species. Three approaches for measuring total oxidative potential were compared. These include using methanol as the solvent with (1) and without (2) filtering the extract, followed by removing the solvent and reconstituting with water, and (3) extraction in pure water and performing the OP analysis in the extraction vial with the filter. The water extraction method (the third approach, with filter remaining in the vial) generally yielded the highest DTT responses with better precision (coefficient of variation of 1-5 %) and was correlated with a greater number of other aerosol components. Because no organic solvents were used, which must be mostly eliminated prior to DTT analysis, it was easiest to automate by modifying an automated analytical system for measuring water-soluble OP developed by . Therefore, the third method was applied to the field study for the determination of total OP. Daily 23 h filter samples were collected simultaneously at a roadside (RS) and a representative urban (Georgia Tech, GT) site for two 1-month study periods, and both water-soluble (OP WS-DTT ) and total (OP Total-DTT ) OP were measured. Using PM 2.5 (aerodynamic diameter < 2.5 µm) high-volume samplers with quartz filters, the OP WS-DTT -to-OP Total-DTT ratio at the urban site was 65 % with a correlation coefficient (r) of 0.71 (N = 35; p value < 0.01), compared to a ratio of 62 % and r = 0.56 (N = 31; p value < 0.01) at the roadside site. The same DTT analyses were performed, and similar results were found using particle composition monitors (flow rate of 16.7 L min −1 ) with Teflon filters. Comparison of measurements between sites showed only slightly higher levels of both OP WS-DTT and OP Total-DTT at the RS site, indicating both OP WS-DTT and OP Total-DTT were largely spatially homogeneous. These results are consistent with roadway emissions as sources of DTT-quantified PM 2.5 OP and indicate that both soluble and insoluble aerosol components contributing to OP are largely secondary.

Ambient particulate matter may upset redox homeostasis, leading to oxidative stress and adverse health effects. Size distributions of water-insoluble and water-soluble OPDTT (dithiothreitol assay, measure of oxidative potential per air volume) are reported for a roadside site and an urban site. The average water-insoluble fractions were 23% and 51%, and 37% and 39%, for fine and coarse modes at the roadside and urban sites, respectively, measured during different periods. Water-soluble OPDTT was unimodal, peaked near 1–2.5 μm due to contributions from fine-mode organic components plus coarse-mode transition metal ions. In contrast, water-insoluble OPDTT was bimodal, with both fine and coarse modes. The main chemical components that drive both fractions appear to be the same, except that for water-insoluble OPDTT the compounds were absorbed on surfaces of soot and non-tailpipe traffic dust. They were largely externally mixed and deposited in different regions in the respiratory system, transition metal ions predominately in the upper regions and organic species, such as quinones, deeper in the lung. Although OPDTT per mass (toxicity) was highest for ultrafine particles, estimated lung deposition was mainly from accumulation and coarse particles. Contrasts in the phases of these forms of OPDTT deposited in the respiratory system may have differing health impacts.

Exposure to air pollution is a leading global health risk. Secondary organic aerosol (SOA) constitute a large portion of ambient particulate matter (PM). In this study, the water-soluble oxidative potential (OP) determined by dithiothreitol (DTT) consumption and intracellular reactive oxygen and nitrogen species (ROS/RNS) production was measured for SOA generated from the photooxidation of naphthalene in the presence of iron sulfate and ammonium sulfate seed particles. The measured intrinsic OP varied for aerosol formed using different initial naphthalene concentrations, however, no trends were observed between OP and bulk aerosol composition or seed type. For all experiments, aerosol generated in the presence of iron-containing seed induced higher ROS/RNS production compared to that formed in the presence of inorganic seed. This effect was primarily attributed to differences in aerosol carbon oxidation state . In the presence of iron, radical concentrations are elevated via iron redox cycling, resulting in more oxidized species. An exponential trend was also observed between ROS/RNS and for all naphthalene SOA, regardless of seed type or aerosol formation condition. This may have important implications as aerosol have an atmospheric lifetime of a week, over which increases due to continued photochemical aging, potentially resulting in more toxic aerosol.