XPS surface chemical characterization of atmospheric particles of different sizes

Surface chemical composition of particles has a key role in determining the reactivity and optical properties of atmospheric aerosol. This composition depend on the particles sources and formation processes and it influences human health and climate. In this work, the X-ray photoelectron spectroscopy (XPS) has been used for the systematic surface characterization of atmospheric particles of different sizes, collected using a 10-stage MOUDI-II rotating cascade impactor in an urban background site. The high resolution XPS spectra allowed to distinguish different organic functional groups (C-C/CC, -C-O, -CO/-C(O)N, -C(O)O, C-O3=) and to speciate the detectable hetero-elements, sulphur (S-O42-, sulphone and sulphide compounds), nitrogen (N-H4+, N-O3-, N-O2- and organic-nitrogen compounds), sodium (Na⁺) and chlorine (Cl^-) species. Significant differences in particles belonging to accumulation (small particles) and coarse (large particles) modes were observed being due to the formation processes and sources from which particles originated. The oxygen concentrations is inversely correlated with carbon concentrations, however, the content of oxidized organic carbon is not correlated with oxygen content confirming that the oxygen increment observed in large particles can likely be attributed to the contribution of inorganic species (crustal origin). The speciation of nitrogen showed ammonium only in the accumulation mode and nitrate only in coarse mode excluding the presence of ammonium nitrate of secondary origin in the area studied. A correlation of Na and Cl was attributed to the marine contribution with an excess of Cl on the surface correlated with the depletion of Cl observed in the bulk of particles.