Atmospheric gaseous HNO 3, particulate nitrate, and aerosol size distributions of major ionic species at a rural site in western Germany

Abstract

Nitric acid and particulate nitrate in addition to other trace species were measured in the air at Deuselbach, a rural site in western Germany, in June and July 1985 under background atmospheric conditions. High-volume open face triple filter packs and cascade impactors were used together with ion-chromatographic analyses. Laboratory tests showed good correspondence between gaseous nitric acid and nitrate deposited on nylon back-up filters for low ambient aerosol concentrations as observed in the field. High aerosol loadings typically found in Mainz caused part of nitric acid to be retained together with particulate nitrate on the teflon front filter. The concentration of nitric acid observed in the field went through a maximum during the day and a minimum at night with a clear anti-correlation with relative humidity. For r.h. ⩽ 60% the average fraction of gaseous to total nitrate was 39 ± 8%. The average fraction from all data was 22%. The molar fraction of total nitrate to nitrogen dioxide was 24%. It is shown that the diurnal variation of HNO 3 is partly due to absorption by liquid water associated with the aerosol, which increases with rising relative humidity (at night). The absorption is significant only because solution pH is buffered by the presence of sulfate and the formation of bisulfate. Most of the field data showed particulate nitrate to occur primarily in the coarse size range ( ⩾ 2 μm diameter) with sodium providing the main cation. Sea salt was identified as the principal source of sodium. Ammonium nitrate occurred only sporadically in the fine particle mode ( ⩽ 2 pm diameter). Ammonium nitrate was largely absent because the product of the concentrations of nitric acid (observed) and ammonia (inferred) was below the minimum required for equilibrium concentrations of particulate NH 4NO 3 to form. In addition, there often was insufficient ammonium (and other measurable cations) present in fine particles to balance the amount of sulfate.