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.