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

Abstract. A photochemical box model constrained by ancillary observations was used to simulate OH and HO₂ concentrations for three days of ambient observations during the HO_xComp field campaign held in Jülich, 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 Chemistry Mechanism with updated isoprene chemistry adapted from Master Chemical Mechanism ver. 3.1) with high R² values (0.72–0.97) over a range of isoprene (0.3–2 ppb) and NO (0.1–10 ppb) mixing ratios. Daytime HO₂(*) levels, reconstructed from the base model results taking into account the sensitivity toward speciated RO₂ (organic peroxy) radicals, as recently reported from one of the participating instruments in the HO₂ measurement mode, were 93% higher than the observations made by the single instrument. This also indicates an overprediction of the HO₂ to OH recycling. Together with the good model-measurement agreement for OH, it implies a missing OH source in the model. Modeled OH and HO₂(*) could only be matched to the observations by addition of a strong unknown loss process for HO₂(*) that recycles OH at a high yield. Adding to the base model, instead, the recently proposed isomerization mechanism of isoprene peroxy radicals (Peeters and Müller, 2010) increased OH and HO₂(*) 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 HO₂(*) 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 isoprene concentrations (∼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 HO₂(*). We found that this tendency is associated with high NO_x concentrations, suggesting that some HO₂ production or regeneration processes under high NO_x conditions were being overlooked; this might require revision of ozone production regimes.