This paper describes how a two-step chemical fractionation method that allows the determination of 17 elements in airborne particulate matter, has been applied to a monitoring campaign of PM10 and PM2.5 in the Lazio region (Italy). This method involved an extraction in a pH buffered aqueous solution followed by a microwave-assisted acid digestion of the residue. With respect to the determination of the total elemental contents, the evaluation of a soluble fraction provides more reliable information on the presence and of the destiny of heavy metals in the environment. Furthermore, the pH buffered extraction conditions chosen, rendered the results independent of the intrinsic acidity of the collected samples and, although the chemical fractionation has a purely operational function, it facilitates the study of the relationship between the distribution of solubility and the different emission sources. Results are discussed in relation to the different concentration and the different degrees of solubility of the elements observed in two sampling sites; one in an urban and one in a rural environment. Since in-parallel sampling of PM2.5 and PM10 were performed in both sites, the influence of particle size is also discussed. Behaviour of some tracers deriving from both vehicular traffic, with particular attention to re-suspended road dusts, and naturally generated particulate matter, such as marine aerosol and Saharian dust, are discussed.