The effects of reactant concentration and air flow rate in the consumption of dissolved O₂ during the photochemistry of aqueous pyruvic acid

The sunlight photochemistry of the organic chromophore pyruvic acid (PA) in water generates ketyl and acetyl radicals that contribute to the production and processing of atmospheric aerosols. The photochemical mechanism is highly sensitive to dissolved oxygen content, [O₂(aq)], among other environmental conditions. Thus, herein we investigate the photolysis (λ ≥ 305 nm) of 10–200 mM PA at pH 1.0 in water covering the relevant range 0 ≤ [O₂(aq)] ≤ 1.3 mM. The rapid consumption of dissolved oxygen by the intermediate photolytic radicals is monitored in real time with a dissolved oxygen electrode. In addition, the rate of O₂(aq) consumption is studied at air flow rates from 30.0 to 900.0 mL min⁻¹. For the range of [PA]₀ covered under air saturated conditions and 30 mL min⁻¹ flow of air in this setup, the estimated half-lives of O₂(aq) consumed by the photolytic radicals fall within the interval from 22 to 3 min. Therefore, the corresponding depths of penetration of O₂(g) into water (x = 4.3 and 1.6 µm) are determined, suggesting that accumulation and small coarse mode aqueous particles should not be O₂-depleted in the presence of sunlight photons impinging this kind of chromophore. These photochemical results are of major tropospheric relevance for understanding the formation and growth of secondary organic aerosol.