The mutagenicity of urine extracts from anode plant workers exposed to coal tar pitch volatiles and non-smoking psoriatic patients treated with coal tar applications and UV light (Goeckermann regimen), was determined by the plate incorporation assay and the fluctuation test employing Salmonella typhimurium strain TA98 in the presence of rat liver post-mitochondrial fractions and deconjugating enzymes. The levels of total polycyclic aromatic hydrocarbons (PAHs) and of a marker metabolite of pyrene (1-hydroxypyrene) were determined in the urine of the same subjects. Both the occupational and in particular the therapeutic exposure to coal tar resulted in clear increases in urinary levels of PAH metabolites as compared to unexposed subjects. The level of 1-hydroxypyrene in the urine samples was comparable to or even greater than the corresponding level of total PAHs, indicating a poor recovery of PAH metabolites for this method. Following treatment with coal tar, most of the psoriatic patients excreted clearly increased levels of mutagens in their urine, while non-smoking anode plant workers showed no increase in urinary mutagenicity. The minimum levels of PAH metabolites corresponding to a significant increase in urinary mutagenicity varied from sample to sample, presumably depending on interfering factors present in different amounts in the extracts. Nonetheless the urine samples which were clearly mutagenic presented elevated levels of PAH metabolites, suggesting that the mutagenicity assays lack sufficient sensitivity to allow their application in the biological monitoring of most occupational exposures to coal tar.