Photochemical production and loss rates of ozone at Sable Island, Nova Scotia during the North Atlantic Regional Experiment (NARE) 1993 summer intensive

Abstract

Three weeks of summertime surface-based chemical and meteorological observations at Sable Island, Nova Scotia during the North Atlantic Regional Experiment (NARE) 1993 summer intensive are used to study instantaneous photochemical production and loss rates of ozone by means of a numerical photochemical model. Results are most sensitive to the averaging scheme of data used to constrain the model and the ambient variability of the measurements. Model simulations driven by a time series of 5 min averaged data, most representative of the chemistry at the site, yield an average net photochemical ozone production of 3.6 ppbv/d. Estimates of net ozone production designed to filter out local sources, by using 1000–1400 LT median values of observations to drive the model and by excluding short-lived hydrocarbons, give values ranging from 1 to 4 ppbv/d. These positive values of net ozone production within the marine boundary layer over Sable Island demonstrate the impact of polluted continental plumes on the background photochemistry of the region during the intensive. The dominant ambient variables controlling photochemical production and loss rates of ozone at the site during the measurement campaign appear to be levels of nitrogen oxides, ozone, nonmethane hydrocarbons, and solar intensity determined by cloud cover. The model partitioning of nitrogen oxides agrees for the most part with measurements, lending credence to calculated photochemical production and loss rates of ozone as well as inferred levels of peroxy radicals not measured at the site. Discrepancies, however, often occur during episodes of intermittent cloud cover, fog, and rain, suggesting the influence of cloud processes on air masses reaching the site.