Assessment of the link between atmospheric dispersion and chemical composition of PM₁₀ at 2-h time resolution

The concentration of air pollutants is governed by both emission rate and atmospheric dispersion conditions. The role played by the atmospheric mixing height in determining the daily time pattern of PM components at the time resolution of 2 h was studied during 21 days of observation selected from a 2-month field campaign carried out in the urban area of Rome, Italy. Natural radioactivity was used to obtain information about the mixing properties of the lower atmosphere throughout the day and allowed the identification of advection and stability periods. PM₁₀ composition was determined by X-ray fluorescence, ion chromatography, inductively coupled plasma-mass spectrometry and thermo-optical analysis. A satisfactory mass closure was obtained on a 2-h basis, and the time pattern of the PM₁₀ macro-sources (soil, sea, secondary inorganics, organics, traffic exhaust) was acquired at the same time scale. After a complete quality control procedure, 27 main components and source tracers were selected for further elaboration. On this database, we identified some groups of co-varying species related to the main sources of PM. Each group showed a peculiar behaviour in relation to the mixing depth. PM components released by soil, biomass burning and traffic exhaust, and, particularly, ammonium nitrate, showed a clear dependence on the mixing properties of the lower atmosphere. Biomass burning components and organics peaked during the night hours (around midnight), following the atmospheric stabilization and increased emission rate. Traffic exhausts and non-exhausts species also peaked in the evening, but they showed a second, minor increase between 6:00 and 10:00 when the strengthening of the emission rate (morning rush hour) was counterbalanced by the dilution of the atmosphere (increasing mixing depth). In the case of ammonium nitrate, high concentrations were kept during the whole night and morning.