Peroxy radicals in the summer free troposphere: seasonality and potential for heterogeneous loss

The sum of peroxy radicals (HO<sub>2</sub>+Σ<sub><i>i</i></sub>R<sub><i>i</i></sub>O<sub>2</sub>) and supporting trace gases were measured on the Jungfraujoch (3580 m a.s.l.) during the late summer of 2005. The period was marked by extended times of heavy snow which led to reduction in the observed peroxy radicals during the snowy periods that was greater than the concomitant reduction in <i>j</i>(O<sup>1</sup>D). In the limit a first order loss rate of 0.0063 s<sup>−1</sup> can be derived for the peroxy radical loss in the snowy conditions that could be potentially ascribed to a heterogenous loss process. On snow free days photolysis of HCHO is shown to be a significant peroxy radical source. The seasonal trends of the peroxy radical concentrations have been mapped from the winter to summer transition in line with previous experiments. Net ozone production in late summer at the Jungfraujoch was net neutral to marginally ozone destructive. A value of 28±4 pptv is calculated for the ozone compensation point for the snow free days

Intercomparison of oxygenated volatile organic compound measurements at the SAPHIR atmosphere simulation chamber

This paper presents results from the first large-scale in situ intercomparison of oxygenated volatile organic compound (OVOC) measurements. The intercomparison was conducted blind at the large (270 m(3)) simulation chamber, Simulation of Atmospheric Photochemistry in a Large Reaction Chamber (SAPHIR), in Julich, Germany. Fifteen analytical instruments, representing a wide range of techniques, were challenged with measuring atmospherically relevant OVOC species and toluene (14 species, C-1 to C-7) in the approximate range of 0.5-10 ppbv under three different conditions: (1) OVOCs with no humidity or ozone, (2) OVOCs with humidity added (r.h. approximate to 50%), and (3) OVOCs with ozone (approximate to 60 ppbv) and humidity (r.h. approximate to 50%). The SAPHIR chamber proved to be an excellent facility for conducting this experiment. Measurements from individual instruments were compared to mixing ratios calculated from the chamber volume and the known amount of OVOC injected into the chamber. Benzaldehyde and 1-butanol, compounds with the lowest vapor pressure of those studied, presented the most overall difficulty because of a less than quantitative transfer through some of the participants' analytical systems. The performance of each individual instrument is evaluated with respect to reference values in terms of time series and correlation plots for each compound under the three measurement conditions. A few of the instruments performed very well, closely matching the reference values, and all techniques demonstrated the potential for quantitative OVOC measurements. However, this study showed that nonzero offsets are present for specific compounds in a number of instruments and overall improvements are necessary for the majority of the techniques evaluated here