OH and HO2 radical chemistry in a midlatitude forest: Measurements and model comparisons

Reactions of the hydroxyl (OH) and peroxy (HO2 and RO2) radicals play a central role in the chemistry of the atmosphere. In addition to controlling the lifetimes of many trace gases important to issues of global climate change, OH radical reactions initiate the oxidation of volatile organic compounds (VOCs) which can lead to the production of ozone and secondary organic aerosols in the atmosphere. Previous measurements of these radicals in forest environments characterized by high mixing ratios of isoprene and low mixing ratios of nitrogen oxides (NOx ) (typically less than 1 2 ppb) have shown serious discrepancies with modeled concentrations. These results bring into question our understanding of the atmospheric chemistry of isoprene and other biogenic VOCs under low NOx conditions. During the summer of 2015, OH and HO2 radical concentrations, as well as total OH reactivity, were measured using laser-induced fluorescence fluorescence assay by gas expansion (LIF-FAGE) techniques as part of the Indiana Radical Reactivity and Ozone productioN InterComparison (IRRONIC). This campaign took place in a forested area near Indiana University s Bloomington campus which is characterized by high mixing ratios of isoprene (average daily maximum of approximately 4 ppb at 28 °C) and low mixing ratios of NO (diurnal average of approximately 170 ppt). Supporting measurements of photolysis rates, VOCs, NOx , and other species were used to constrain a zero-dimensional box model based on the Regional Atmospheric Chemistry Mechanism (RACM2) and the Master Chemical Mechanism (MCM 3.2), including versions of the Leuven isoprene mechanism (LIM1) for HOx regeneration (RACM2- LIM1 and MCM 3.3.1). Using an OH chemical scavenger technique, the study revealed the presence of an interference with the LIF-FAGE measurements of OH that increased with both ambient concentrations of ozone and temperature with an average daytime maximum equivalent OH concentration of approximately 5±106 cm3. Subtraction of the interference resulted in measured OH concentrations of approximately 4±106 cm3 (average daytime maximum) that were in better agreement with model predictions although the models underestimated the measurements in the evening. The addition of versions of the LIM1 mechanism increased the base RACM2 and MCM 3.2 modeled OH concentrations by approximately 20% and 13 %, respectively, with the RACM2-LIM1 mechanism providing the best agreement with the measured concentrations, predicting maximum daily OH concentrations to within 30% of the measured concentrations. Measurements of HO2 concentrations during the campaign (approximately a 1±109 cm3 average daytime maximum) included a fraction of isoprene-based peroxy radicals (HO2 D HO2 C-RO2) and were found to agree with model predictions to within 10 % 30 %. On average, the measured reactivity was consistent with that calculated from measured OH sinks to within 20 %, with modeled oxidation products accounting for the missing reactivity, however significant missing reactivity (approximately 40% of the total measured reactivity) was observed on some days. © 2020 International Union of Crystallography. All rights reserved