Peroxy radicals during BERLIOZ at Pabstthum: Measurements, radical budgets and ozone production

Abstract

The Photochemistry Experiment during BERLIOZ (PHOEBE) was conducted in July and August 1998 at a rural site located near the small village of Pabstthum, about 50 km northwest of downtown Berlin. In this paper, spectroscopic measurements of hydroxyl (OH) and peroxy radicals (HO 2 and RO 2 ) are discussed for two intensive days (20 and 21 July) of the campaign. On both days peak values of the radical concentrations were similar, reaching 6–8 × 10 6 cm −3 for OH and 20–30 ppt for RO 2 and HO 2 . Fairly high OH concentrations were observed during the morning hours in the presence of high‐NO x mixing ratios (>20ppb). The “master chemical mechanism” (MCM) was used to calculate OH, HO 2 , and RO 2 concentrations from the simultaneously measured data comprising a comprehensive set of speciated hydrocarbons and carbonyl compounds, O 3 , CO, NO, NO 2 , HONO, PAN, J(NO 2 ), J(O 1 D), and meteorological parameters. The calculated OH concentrations are in excellent agreement with the measurements during the morning hours at high‐NO x (>10 ppb). However, at low NO x conditions the model overestimates OH by a factor 1.6. The modeled concentrations of HO 2 and RO 2 are in reasonable agreement with the measurements on 20 July. On the next day, when isoprene from nearby sources was the dominant VOC, the model overpredicted HO 2 and RO 2 in addition to OH. Radical budgets solely calculated from measured data show that a missing sink for OH must be responsible for the overestimation by MCM. Missing VOC reactivity is unlikely, unless these VOC would not lead to RO 2 production upon reaction with OH. The measured RO 2 /HO 2 ratio of about one is well reproduced by the MCM, whereas a simple model without recycling of RO 2 from decomposition and isomerisation of alkoxy radicals underpredicts the measured ratio by about a factor of two. This finding highlights the importance of RO 2 recycling in the chemical mechanism. The ozone production rate P(O 3 ), calculated from the peroxy radical concentrations and NO, had a maximum of 8 ppb/hr at 0.5 ppb NO, which is in good agreement with results from previous campaigns at Tenerife and Schauinsland.