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Exposure to particulate matter results in adverse health outcomes, especially in sensitive members of the community. Many communities that co-exist with industry are concerned about the perceived impact of emissions from that industry on their health. Such concerns have resulted in two studies in the Hunter Valley of New South Wales, Australia. The chemical composition of samples of particulate matter, collected over two 12-month sampling periods (2012 and 2014–2015) at six sites in the Hunter Valley and across two size fractions (PM2.5 and PM2.5–10) were input to a receptor model to determine the source of particulate matter influencing particle composition at the sites. Fourteen factors were found to contribute to particle mass. Of these, three source profiles common to all sites, size fractions, and sampling periods were sea salt, industry-aged sea salt and soil. Four source profiles were common across all sites for PM2.5 including secondary sulphate, secondary nitrate, mixed industry/vehicles, and woodsmoke. One source profile (other biomass smoke) was only identified in PM2.5 at Singleton and Muswellbrook, two source profiles (mixed industry/shipping and vehicles) were only identified in PM2.5 at Newcastle, Beresfield, Mayfield, and Stockton, and one source (primary nitrate) was only identified at Stockton in PM2.5. Three sources (bioaerosol, light absorbing particles (coal dust), and industry) were only identified in the PM2.5–10 size fraction at Mayfield and Stockton. The contribution of the soil factor to PM2.5 mass was consistent across the sites, while the fresh sea salt factor decreased with distance from the coast from 23% at Stockton to 3% at Muswellbrook, and smoke increased with distance from the coast. Primary industry was greatest at Stockton (due to the influence of ammonium nitrate emitted from a prilling tower) and lowest inland at Muswellbrook. In general, primary emissions across the sites accounted for 30% of the industry sources. The largest contribution to PM2.5 was from secondary sources at all sites except at Muswellbrook, where woodsmoke and industry sources each made an equal contribution of 40%. In general, secondary reactions accounted for approximately 70% of the industry source, although at Stockton, with the presence of the prilling tower, this split was 50% primary and 50% secondary and at Muswellbrook, the split was 20% primary and 80% secondary. These findings add to the evidence base required to inform policies and programs that will improve air quality in the Hunter Valley. [ABSTRACT FROM AUTHOR]