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The possibility to discriminate between different emission sources and between natural and anthropogenic contributions is a key issue for planning efficient air pollution reduction and mitigation strategies. Moreover, the knowledge of the particulate matter (PM) chemical composition for the different size fractions is recognized as increasingly important, in particular with respect to health effects of exposed population. This study is focused on the characterization of PM₁₀ and PM_2.5 main sources located in the Civitavecchia harbor-industrial area (Central Italy), namely a large coal-fired power plant, a natural gas power plant, the harbor area, the vehicular traffic (due to both the local traffic and the highway crossing the area) and small industrial activities. The approach was based on PM₁₀/PM_2.5 samples monthly collected for one year and a further relative chemical characterization of organic and inorganic fractions. Wind-select sensors, allowing a selective PM₁₀ and PM_2.5 sampling downwind to specific emission sources, were used for the overall sampling. This methodology manages to explain specific emission patterns and to assess the concentration levels of the micro pollutants emitted by local sources and particularly toxic for health. A descriptive statistical analysis of data was performed, also verifying the occurrence of legislative threshold exceedances. Moreover, in order to highlight the contribution of specific sources, the differences in the measured micro pollutants concentrations between wind directions, PM size fractions and sampling sites have been investigated, as well as the seasonal trends of pollutants concentrations. These results allow to highlight that the applied methodology represents a valid support in source apportionment studies.