A seasonal comparison of the ozone photochemistry in clean and polluted air masses at Mace Head, Ireland

Abstract

Measurements of the sum of peroxy radicals [HO2 + RO2], NOx (NO + NO2) and NOy (the sum of oxidised nitrogen species) made at Mace Head, on the Atlantic coast of Ireland in summer 1996 and spring 1997 are presented. Together with a suite of ancillary measurements, including the photolysis frequencies of O3 → O(1D) (j(O1D)) and NO2 (j(NO2)), the measured peroxy radicals are used to calculate mean daily ozone tendency (defined as the difference of the in-situ photochemical ozone production and loss rates); these values are compared with values derived from the photochemical stationary state (PSS) expression. Although the correlation between the two sets of values is good, the PSS values are found to be significantly larger than those derived from the peroxy radical measurements, on average, in line with previous published work. Possible sources of error in these calculations are discussed in detail. The data are further divided up into five wind sectors, according to the instantaneous wind direction measured at the research station. Calculation of mean ozone tendencies by wind sector shows that ozone productivity was higher during spring (April-May) 1997 than during summer (July-August) 1996 across all air masses, suggesting that tropospheric photochemistry plays an important role in the widely-reported spring ozone maximum in the Northern Hemisphere. Ozone tendencies were close to zero for the relatively unpolluted southwest, west and north-west wind sectors in the summer campaign, whereas ozone productivity was greatest in the polluted south-east sector for both campaigns. Daytime weighted average ozone tendencies were +(0.3 ± 0.1) ppbv h-1 for summer 1996 and +(1.0 ± 0.5) ppbv h-1 for spring 1997. These figures reflect the higher mixing ratios of ozone precursors in spring overall, as well as the higher proportion of polluted air masses from the south-east arriving at the site during the spring campaign. The ozone compensation point, where photochemical ozone destruction and production processes are in balance, is calculated to be ca. 14 pptv NO for both campaigns.