Peroxy radical and related trace gas measurements in the boundary layer above the Atlantic Ocean

Measurements of peroxy radicals (RO2*=HO2+Sigma RO2, where HO2 is the hydroperoxyl radical and R is an organic group) were made using the chemical amplifier technique (PERCA) during the Air chemistry and Lidar studies of tropospheric and stratospheric species on the Atlantic Ocean (ALBATROSS) campaign on board the German research vessel Polarstern (cruise ANT XIV/1, 1996). The data obtained are compared to previous results from an earlier cruise in 1991 (ANT X/1). Reasonable agreement between the two data sets was observed, indicating the reliability of these measurements. Both data sets take into account the sensitivity of the radical amplifier to the presence of ambient water vapor. Maximum RO2* mixing ratios around noon between 40 and 80 pptv were measured. Nighttime signals were observed on many days. Air masses in different latitude regions in the North and South Atlantic could be characterized using back trajectories. In spite of the fact that the RO2* is relatively short lived, its mixing ratio appears to be influenced by the path traveled by the air mass somewhat higher levels being associated with sources of pollution. A box model based on CH4 and CO oxidation chemistry describes RO2* reasonably well but could not explain the persistent nighttime signals and the HCHO observed. An additional soul ce of HCHO is required, indicating the importance of nonmethane hydrocarbon (NMHC) chemistry in the remote Atlantic boundary layer. Both back trajectories and variations of trace gas concentrations indicate that biomass burning, ship, and natural emissions are likely responsible for the observed deviations from the assumed chemistry.