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Abstract. The hydroxyl (OH), hydroperoxy (HO2), and organic peroxy (RO2)radicals play important roles in atmospheric chemistry. In the presence ofnitrogen oxides (NOx), reactions between OH and volatile organiccompounds (VOCs) can initiate a radical propagation cycle that leads to theproduction of ozone and secondary organic aerosols. Previous measurements ofthese radicals under low-NOx conditions in forested environmentscharacterized by emissions of biogenic VOCs, including isoprene andmonoterpenes, have shown discrepancies with modeled concentrations. During the summer of 2016, OH, HO2, and RO2 radical concentrationswere measured as part of the Program for Research on Oxidants:Photochemistry, Emissions, and Transport – Atmospheric Measurements ofOxidants in Summer (PROPHET-AMOS) campaign in a midlatitude deciduousbroadleaf forest. Measurements of OH and HO2 were made by laser-inducedfluorescence–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 ofphotolysis frequencies, VOCs, NOx, O3, and meteorological datawere used to constrain a zero-dimensional box model utilizing either theRegional Atmospheric Chemical Mechanism (RACM2) or the Master ChemicalMechanism (MCM). Model simulations tested the influence of HOxregeneration reactions within the isoprene oxidation scheme from the LeuvenIsoprene Mechanism (LIM1). On average, the LIM1 models overestimated daytimemaximum measurements by approximately 40 % for OH, 65 % for HO2,and more than a factor of 2 for XO2. Modeled XO2 mixing ratioswere also significantly higher than measured at night. Addition of RO2 + RO2 accretion reactions for terpene-derived RO2 radicals tothe model can partially explain the discrepancy between measurements andmodeled peroxy radical concentrations at night but cannot explain thedaytime discrepancies when OH reactivity is dominated by isoprene. Themodels also overestimated measured concentrations of isoprene-derivedhydroxyhydroperoxides (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 radicalsimproves the agreement with the measured ISOPOOH concentrations, suggestingthat the measured radical concentrations are more consistent with themeasured ISOPOOH concentrations. These results suggest that the models maybe missing an important daytime radical sink and could be overestimating therate of ozone and secondary product formation in this forest. 

Abstract. The atmospheric multiphase reaction of dinitrogenpentoxide (N2O5) with chloride-containing aerosol particlesproduces nitryl chloride (ClNO2), which has been observed across theglobe. The photolysis of ClNO2 produces chlorine radicals and nitrogendioxide (NO2), which alter pollutant fates and air quality. However,the effects of local meteorology on near-surface ClNO2 production arenot yet well understood, as most observational and modeling studies focus onperiods of clear conditions. During a field campaign in Kalamazoo, Michigan,from January–February 2018, N2O5 and ClNO2 were measuredusing chemical ionization mass spectrometry, with simultaneous measurementsof atmospheric particulate matter and meteorological parameters. We examinethe impacts of atmospheric turbulence, precipitation (snow, rain) and fog,and ground cover (snow-covered and bare ground) on the abundances ofClNO2 and N2O5. N2O5 mole ratios were lowest duringperiods of lower turbulence and were not statistically significantlydifferent between snow-covered and bare ground. In contrast, ClNO2 moleratios were highest, on average, over snow-covered ground, due to salinesnowpack ClNO2 production. Both N2O5 and ClNO2 moleratios were lowest, on average, during rainfall and fog because ofscavenging, with N2O5 scavenging by fog droplets likelycontributing to observed increased particulate nitrate concentrations. Theseobservations, specifically those during active precipitation and withsnow-covered ground, highlight important processes, including N2O5and ClNO2 wet scavenging, fog nitrate production, and snowpackClNO2 production, that govern the variability in observed atmosphericchlorine and nitrogen chemistry and are missed when considering only clearconditions.