Uptake of isoprene, methacrylic acid and methyl methacrylate into aqueous solutions of sulfuric acid and hydrogen peroxide

Multiphase acid-catalyzed oxidation by hydrogen peroxide has been suggested to be a potential route to secondary organic aerosol formation from isoprene and its gas-phase oxidation products, but the lack of kinetics data significantly limited the evaluation of this process in the atmosphere. Here we report the first measurement of the uptake of isoprene, methacrylic acid and methyl methacrylate into aqueous solutions of sulfuric acid and hydrogen peroxide. Isoprene cannot readily partition into the solution because of its high volatility and low solubility, which hinders its further liquid-phase oxidation. Both methacrylic acid and methyl methacrylate can enter the solutions and be oxidized by hydrogen peroxide, and steady-state uptake was observed with the acidity of solution above 30 wt.% and 70 wt.%, respectively. The steady-state uptake coefficient of methacrylic acid is much larger than that of methyl methacrylate for a solution with same acidity. These observations can be explained by the different reactivity of these two compounds caused by the different electron-withdrawing conjugation between carboxyl and ester groups. The atmospheric lifetimes were estimated based on the calculated steady-state uptake coefficients. These results demonstrate that the multiphase acid-catalyzed oxidation of methacrylic acid plays a role in secondary organic aerosol formation, but for isoprene and methyl methacrylate, this process is not important in the troposphere.

A critical review of sulfate aerosol formation mechanisms during winter polluted periods

Sulfate aerosol contributes to particulate matter pollution and plays a key role in aerosol radiative forcing,impacting human health and climate change.Atmospheric models tend to substantially underestimate sulfate concentrations during haze episodes,indicating that there are still missing mechanisms not considered by the models.Despite recent good progress in understanding the missing sulfate sources,knowledge on different sulfate formation pathways during polluted periods still involves large uncertainties and the dominant mechanism is under heated debate,calling for more field,laboratory,and modeling work.Here,we review the traditional sulfate formation mechanisms in cloud water and also discuss the potential factors affecting multiphase S(Ⅳ)oxidation.Then recent progress in multiphase S(Ⅳ)oxidation mechanisms is summarized.Sulfate formation rates by different prevailing oxidation pathways under typical winter-haze conditions are also calculated and compared.Based on the literature reviewed,we put forward control of the atmospheric oxidation capacity as a means to abate sulfate aerosol pollution.Finally,we conclude with a concise set of research priorities for improving our understanding of sulfate formation mechanisms during polluted periods.