A variety of polycyclic aromatic hydrocarbon (PAH) diagnostic ratios were examined as source apportionment tools in the analysis of a PAH data set associated with atmospheric particulate matter collected in an urban-industrial environment. Seventy-six PM₁₀ samples were collected concurrently at 4 sampling sites over a one-month period in Hamilton, Ontario, Canada, a city of 500 000 people that is home to two integrated steel companies, associated industries and a network of roadways and major highways. Samples collected under well defined meteorological conditions were categorized as being ‘upwind’ or ‘downwind’ of the industrial sector. All sample extracts were analyzed for 48 parent PAH, methylphenanthrenes and sulfur-containing aromatics and showed a thousand-fold range of total PAH concentrations (0.23–172 ng m⁻³). Of all PAH diagnostic ratios examined, the two most useful were the anthracene/(anthracene+phenanthrene) and benz[a]anthracene/(benz[a]anthracene+chrysene/triphenylene) ratios. These afforded the best discrimination of samples that had significant industrial impacts. This work is the first example of the use of a linear combination of PAH ratios, coupled with total PAH data and well defined local samples to determine the relative impacts of mobile and industrial emissions in an urban-industrial environment. Use of a linear combination of PAH ratios allowed us to categorize 95% of the data as ‘upwind’ or ‘downwind’ of the industrial sector. It is important to determine PAH ratio threshold values based on data from well defined local samples rather than relying on literature values alone.