Experimental chemical budgets of OH, HO2 and RO2 radicals in rural air in West-Germany during the JULIAC campaign 2019
Authors: Cho Changmin , Fuchs Hendrik , Hofzumahaus Andreas , Holland Frank , Bloss William J. , Bohn Birger , Dorn Hans-Peter , Glowania Marvin , Hohaus Thorsten , Liu Lu , Monks Paul S. , Niether Doreen , Rohrer Franz , Sommariva Roberto , Tan Zhaofeng , Tillmann Ralf , Kiendler-Scharr Astrid , Wahner Andreas , Novelli Anna 
Published: August 2022

Abstract. Photochemical processes in ambient air were studied using the atmospheric simulation chamber SAPHIR at Forschungszentrum Jülich, Germany. Ambient air was continuously drawn into the chamber through a 50 m high inlet line and passed through the chamber for one month in each season throughout 2019. The residence time of the air inside the chamber was about one hour. As the research centre is surrounded by a mixed deciduous forest and is located close to the city Jülich, the sampled air was influenced by both anthropogenic and biogenic emissions. Measurements of hydroxyl (OH), hydroperoxyl (HO2) and organic peroxy (RO2) radicals were achieved by a laser-induced fluorescence instrument. The radical measurements together with measurements of OH reactivity (kOH, the inverse of the OH lifetime) and a comprehensive set of trace gas concentrations and aerosol properties allowed for the investigation of the seasonal and diurnal variation of radical production and destruction pathways. In spring and summer periods, median OH concentrations reached 6 × 106 cm-3 at noon, and median concentrations of both, HO2 and RO2 radicals, were 3 × 108 cm-3. The measured OH reactivity was between 4 and 18 s-1 in both seasons. The total reaction rate of peroxy radicals with NO was found to be consistent with production rates of odd oxygen (OX = NO2+O3) determined from NO2 and O3 concentration measurements. The chemical budgets of radicals were analysed for the spring and summer seasons, when peroxy radical concentrations were above the detection limit. For most conditions, the concentrations of radicals were mainly sustained by the regeneration of OH via reactions of HO2 and RO2 radicals with nitric oxide (NO). The median diurnal profiles of the total radical production and destruction rates showed maxima between 3 to 8 ppbv h-1 for OH, HO2 and RO2. Total ROX (OH, HO2, and RO2) initiation and termination rates were below 3 ppbv h-1. The highest OH radical turnover rate of 13 ppbv h-1 was observed during a high-temperature (max 40°C) period in August. In this period, the highest HO2, RO2 and ROX turnover rates were around 11, 10 and 4 ppbv h-1, respectively. When NO mixing ratios were between 1 ppbv to 3 ppbv, OH and HO2 production and destruction rates were balanced, but unexplained RO2 and ROX production reactions with median rates of 2 ppbv h-1 and 0.4 ppbv h-1, respectively, were required to balance their destruction. For NO mixing ratios above 3 ppbv, the peroxy radical reaction rates with NO were highly uncertain due to the low peroxy radical concentrations close to the limit of NO interferences in the HO2 and RO2 measurements. For NO mixing ratios below 1 ppbv, a missing OH source with a rate of up to 3.0 ppbv h-1 was found. This missing OH source consists likely of a combination of a missing primary radical source (0.5 ~ 1.4 ppbv h-1) and a missing inter-radical HO2 to OH conversion reaction with a rate of up to 2.5 ppbv h-1. The dataset collected in this campaign allowed to analyze the potential impact of OH regeneration from RO2 isomerization reactions from isoprene, HO2 uptake on aerosol, and RO2 production from chlorine chemistry on radical production and destruction rates. These processes were negligible for the chemical conditions encountered in this study.