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© 2019 Elsevier B.V. Knowledge about polar derivatives of polycyclic aromatic hydrocarbons (PAHs) in soils is limited despite the extensive study of the environmental presence and persistence of non-polar parent PAHs. Polar PAHs have greater potential to be more toxic at low environmental concentrations compared to their homocyclic analogues. For both polar and non-polar PAHs, combustion of fossil fuels is often the main source especially in industrialised environments. This study investigated the concentration profiles of PAHs and its associated polar PAHs such as nitrated PAHs (NPAHs), oxygenated PAHs (oxy-PAHs) and nitrogen, sulphur and oxygen heterocyclic PAHs (N/S/O-heterocyclic PAHs) in a well-known industrial heritage city of Australia. The most abundant polar PAHs were 9-fluorenone (oxy-PAHs), 2-nitrofluorene (NPAHs) and carbazole (heterocyclic-PAHs). A positive correlation (r = 0.5, p < 0.01) between ∑13PAHs and ∑19 polar PAHs was observed, implying a possible spatial association between parent and polar PAHs. The concentrations of polar PAHs in soil samples, across various landuse patterns, were used to calculate the excess lifetime cancer risk (ELCR) from incidental ingestion of soils. The computed ELCR values ranged from 8.2*10−7 (industrial soils) to 2.3*10−6 (residential soils), indicating negligible cancer risks. This is the first known study on the occurrence and concentrations of polar and non-polar PAHs in any Australian city, and the results may serve a baseline purpose for improved risk assessment of contaminated sites.