OH, HO₂, and RO₂ radical chemistry in a rural forest environment: measurements, model comparisons, and evidence of a missing radical sink

The hydroxyl (OH), hydroperoxy (HO₂), and organic peroxy (RO₂) radicals play important roles in atmospheric chemistry. In the presence of nitrogen oxides (NOx), reactions between OH and volatile organic compounds (VOCs) can initiate a radical propagation cycle that leads to the production of ozone and secondary organic aerosols. Previous measurements of these radicals under low-NOx conditions in forested environments characterized by emissions of biogenic VOCs, including isoprene and monoterpenes, have shown discrepancies with modeled concentrations. During the summer of 2016, OH, HO₂, and RO₂ radical concentrations were measured as part of the Program for Research on Oxidants: Photochemistry, Emissions, and Transport - Atmospheric Measurements of Oxidants in Summer (PROPHET-AMOS) campaign in a midlatitude deciduous broadleaf forest. Measurements of OH and HO₂ were made by laser-induced fluorescence-fluorescence assay by gas expansion (LIF-FAGE) techniques, and total peroxy radical (XO2) mixing ratios were measured by the Ethane CHemical AMPlifier (ECHAMP) instrument. Supporting measurements of photolysis frequencies, VOCs, NOx, O3, and meteorological data were used to constrain a zero-dimensional box model utilizing either the Regional Atmospheric Chemical Mechanism (RACM2) or the Master Chemical Mechanism (MCM). Model simulations tested the influence of HOx regeneration reactions within the isoprene oxidation scheme from the Leuven Isoprene Mechanism (LIM1). On average, the LIM1 models overestimated daytime maximum measurements by approximately 40 % for OH, 65 % for HO₂, and more than a factor of 2 for XO2. Modeled XO2 mixing ratios were also significantly higher than measured at night. Addition of RO₂ + RO₂ accretion reactions for terpene-derived RO₂ radicals to the model can partially explain the discrepancy between measurements and modeled peroxy radical concentrations at night but cannot explain the daytime discrepancies when OH reactivity is dominated by isoprene. The models also overestimated measured concentrations of isoprene-derived hydroxyhydroperoxides (ISOPOOH) by a factor of 10 during the daytime, consistent with the model overestimation of peroxy radical concentrations. Constraining the model to the measured concentration of peroxy radicals improves the agreement with the measured ISOPOOH concentrations, suggesting that the measured radical concentrations are more consistent with the measured ISOPOOH concentrations. These results suggest that the models may be missing an important daytime radical sink and could be overestimating the rate of ozone and secondary product formation in this forest.