We present an overview of the concentrations and distributions of water-soluble ion species and elemental components in ambient particulate matter for five measurement sites in southern Italy with the aim of investigating the influence of the different site characteristics on PM levels. The sites encompass different characteristics, ranging from urban to coastal and high-altitude remote areas. PM10 and PM2.5 fractions were collected simultaneously using dual channel samplers during the winter period from November 2015 to January 2016 and analyzed for water-soluble ion species, using ion chromatography, and elemental composition, using inductively coupled plasma mass spectrometry (ICP-MS). In all sites, PM2.5 represented the higher contribution to particulate mass, usually more than two times that of the coarse fraction (PM2.5−10). At the coastal site in Capo Granitola (Western Sicily), sea salts constituted about 30% of total PM10 mass. On average, ion species accounted for 30% to 60% of total PM10 mass and 15% to 50% of PM2.5 mass. We found that secondary ion species, i.e., SO42−, NO3− and NH4+ dominated the identifiable components within both PM2.5 and PM10 fractions. The chlorine–sodium ratio was usually lower than that expected from the natural level in sea salt, evidencing aged air masses. At the monitoring site in Naples, a highly urbanized area affected by high levels of anthropogenic source emissions, an increased contribution of ammonium was found, which was imputed to the increased ammonia emissions from industrial combustion sources and road traffic. The concentrations of the investigated elements showed noteworthy differences from one site to another. The PM10 fraction was highly enriched by sources of anthropogenic origin in the samples from the most urbanized areas. In general, the enrichment factors of the elements were similar between the PM10 and PM2.5 fractions, confirming common sources for all elements.
