Comparisons of observed and modeled OH and HO2 concentrations during the ambient measurement period of the HOxComp field campaign

Abstract. A photochemical box modelconstrained by ancillary observations was used to simulate OH and HO 2 concentrations for three days of ambient observations during the HO x Comp field campaign held in Julich, Germany in July 2005. Daytime OH levels observed by four instruments were fairly well reproduced to within 33% by a base model run (Regional Atmospheric ChemistryMechanism with updated isoprenechemistry adapted from Master Chemical Mechanism ver. 3.1) with high R 2 values (0.72–0.97) over a range of isoprene(0.3–2 ppb) and NO (0.1–10 ppb) mixing ratios. Daytime HO 2 (*) levels, reconstructed from the base model results taking into account the sensitivity toward speciated RO 2 (organic peroxy) radicals, as recently reported from one of the participating instruments in the HO 2 measurement mode, were 93% higher than the observations made by the single instrument. This also indicates an overprediction of the HO 2 to OH recycling. Together with the good model-measurement agreement for OH, it implies a missing OH source in the model. Modeled OH and HO 2 (*) could only be matched to the observations by addition of a strong unknown loss process for HO 2 (*) that recycles OH at a high yield. Adding to the base model, instead, the recently proposed isomerization mechanism of isopreneperoxy radicals (Peeters and Muller, 2010) increased OH and HO 2 (*) by 28% and 13% on average. Although these were still only 4% higher than the OH observations made by one of the instruments, larger overestimations (42–70%) occurred with respect to the OH observations made by the other three instruments. The overestimation in OH could be diminished only when reactive alkanes (HC8) were solely introduced to the model to explain the missing fraction of observed OH reactivity. Moreover, the overprediction of HO 2 (*) became even larger than in the base case. These analyses imply that the rates of the isomerization are not readily supported by the ensemble of radical observations. One of the measurement days was characterized by low isopreneconcentrations (∼0.5 ppb) and OH reactivity that was well explained by the observed species, especially before noon. For this selected period, as opposed to the general behavior, the model tended to underestimate HO 2 (*). We found that this tendency is associated with high NO x concentrations, suggesting that some HO 2 production or regeneration processes under high NO x conditions were being overlooked; this might require revision of ozone production regimes.