A study of spatial variability of PM10 elemental components was conducted in Terni city (Central Italy), situated in an intramountain depression characterized by the presence of several particulate matter emission sources. The meteorological conditions of the Terni basin limit the dispersion and enhance the accumulation of atmospheric pollutants. Thanks to the utilization of new smart samplers, used for the first time and working in parallel at 23 sampling sites, spatially resolved data were obtained. Localizations of the samplers were chosen in order to evaluate the impact of different local PM10 sources. Chemical composition of the samples was determined in combination with a chemical fractioning procedure that allowed us to discriminate water-soluble and residual fractions of analyzed elements in which proved to be a valuable approach for increasing selectivity of elements as source tracers. Spatial variability of elements underlined the contribution of local emission sources and the different dispersion capacity of each element. The city of Terni resulted to be an ideal area to test and validate a new experimental method for the acquisition of spatially resolved data providing the possibility to properly evaluate the spatial variability of PM10 and its chemical components.