Observations on gaseous and aerosols components of the atmosphere and their relationships

Abstract

Measurements of sulphur dioxide, ozone, ammonia, and soluble inorganic components of the atmospheric aerosol were made at a site in central southern England. Ammonia, ozone, and nitrate aerosol in winter were shown to exhibit significant diurnal variation. Ozone showed a typical diurnal variability, the magnitude of which was dependent upon wind speed. The lower night-time ozone concentrations at lower wind speeds were attributed to depletion inside nocturnal boundary layers by dry deposition. Ammonia, in contrast, showed a different behaviour, whereby the diurnal cycle was more pronounced at higher wind speeds, indicating that the cycle was unlikely to be the result of dry deposition at night. Ammonia concentrations showed a temperature dependence and the diurnal cycle of ammonia at this site appears to be the result of a temperature-driven emission signal. Of the total reduced nitrogen, NH(x) (NH(x) = NH3 + NH4/+ aerosol), the phase was dominant and it is likely that more than 60% of the boundary layer NH(x) is in this phase. The loss term of ammonia by reaction with acid sulphate aerosol is likely to be greater than that by dry deposition on a UK scale. Nitrate aerosol showed a positive correlation with sodium aerosol, once the effect of mutual correlations with sulphate and ammonium were removed. This correlation effect, in combination with evidence of a marine-oriented directional dependence of nitrate aerosol, and negative non sea-salt chloride aerosol from the same 'marine' sector, shows the potential importance of the formation of sodium nitrate aerosol from reaction of dinitrogen pentoxide, or possibly nitric acid or nitrogen dioxide with sodium chloride aerosol. It is likely that this provides the major route of nitrate into rain, not the scavenging of nitric acid vapour. Aerosol sulphate, nitrate, and ammonium have been measured at Harwell since 1954. Sulphate aerosol increased up until 1976 and has declined subsequently. Nitrate aerosol has increased over the whole period, whereas ammonium aerosol follows a similar pattern to that of sulphate, but with an equivocal direction of trend after 1976. Sulphate, nitrate and ammonium aerosol all show a similar statistically significant seasonality. A historical inventory of ammonia emissions shows a clear correlation with ammonium aerosol.