China has the largest share of global iron and steel production, which is considered to play a significant contribution to air pollution. This study aims to investigate trace element contamination at different fractions of particulate matter (PM) at industrial areas in China. Three PM fractions, PM2.1-9.0, PM1.1-2.1 and PM1.1, were collected from areas surrounding iron and steelmaking plants at Kunming, Wuhan, Nanjing and Ningbo in China. Multiple trace elements and their bioavailability, as well as Pb isotopic compositions, were analysed for identification of contaminants, health risk assessment and source apportionment. Results showed that PM particles in the sites near industrial areas were associated with a range of toxic trace elements, specifically As, Cr(VI), Cd and Mn, and posed significant health risks to humans. The isotopic Pb compositions identified that coal and high temperature metallurgical processes in the steelmaking process were the dominant contributors to local air pollution in these sites. In addition to iron and steelmaking activities, traffic emissions and remote pollution also played a contributing role in PM contamination, confirmed by the differences of Pb isotopic compositions at each PM fraction and statistical results from Preference Ranking Organization Method for Enrichment Evaluations (PROMETHEE) and Geometrical Analysis for Interactive Aid (GAIA). The results presented in this study provide a comprehensive understanding of PM emissions at iron and steelmaking areas, which helps to guide subsequent updates of air pollution control guidelines to efficiently minimise environmental footprint and ensure long term sustainability of the industries.