Mass size distributions of soluble sulfate, nitrate and ammonium in the Madrid urban aerosol

This paper analyzes the mass size distribution of some inorganic species present in the atmospheric aerosol from a field campaign carried out in Madrid throughout a complete year (February 2007–February 2008). Samplings were performed by means of a micro-orifice uniform deposit impactor (MOUDI). Ambient air was sampled during consecutive nocturnal and diurnal periods, and diurnal/nocturnal behaviors were compared for the twenty night-day sampling pairs that were gathered. Annual and seasonal averages were obtained, and some case studies under specific atmospheric conditions are discussed in the paper.Results have shown that the sulfate and ammonium mass was concentrated in the accumulation mode, between 0.18 and 0.56 μm, so that gas-phase and condensation processes for secondary aerosol formation prevailed during the sampling periods in this area. An exception to this behavior was found during a fog event when distributions for these two species were centered in the 0.56–1 and 1–1.8 μm size stages, corresponding to the droplet mode. In most of the samples, the ammonium mass measured in these size ranges was enough or almost enough to neutralize inorganic acidity by formation of ammonium sulfate and nitrate. However, a significant sulfate mass not neutralized by ammonium was found in the impactor backup quartz filter (aerodynamic diameter < 0.056 μm). The concentration of this sulfate and its contribution to the ultrafine fraction mass was higher under good dispersive conditions, prevailing in summer, when particle growth processes are not so favored due to the higher atmospheric dilution factors. The origin of this ultrafine sulfate has been attributed to direct emissions from traffic, associated to the nucleation mode.Regarding the nitrate concentration, it was found higher in the coarse mode than in the accumulation mode on an annual basis. The highest concentrations were measured in winter episodic situations. The marked seasonal variability shown in the accumulation mode by this species is related to the volatility of ammonium nitrate. Among all the studied ions, nitrate also presented the highest differences between the diurnal and nocturnal concentrations in all size ranges. This is probably related to the short time scale required for its formation from gaseous precursors.

► Particulate nitrate, sulfate and ammonium are concentrated in the accumulation range.
► Particulate nitrate has a marked seasonal effect, with maximum value in winter.
► In-cloud sulfate formation and ammonium uptake was observed during a fog event.
► Ultrafine particles (<0.056 μm) were acidic due to a significant mass of sulfate.