In a former study, a German lignite extract exhibited toxicity to Danio rerio and Caenorhabditis elegans and was shown to have mutagenic and dioxin-like activity. Besides the comparatively low content of known toxic polycyclic aromatic hydrocarbons (PAH), highly intensive peaks of m/z 274 and m/z 324 were observed during the chromatographic analysis. These compounds are assumed to be alkylated chrysenes and picenes (3,3,7-trimethyl-1,2,3,4-tetrahydrochrysene, 1,2-(1'-isopropylpropano)-7-methylchrysene and an isomer of the latter, 1,2,9-trimethyl-1,2,3,4-tetrahydropicene and 2,2,9-trimethyl-1,2,3,4-tetrahydropicene). These compounds are intermediates in the diagenetic formation of chrysene and picene from triterpenoids. Due to their general high abundance in lignites and the toxicity observed for the lignite extract, the mechanism-specific toxicity and bioavailability of these compounds were investigated in the present study using the approach of effect-directed analysis. After the separation of the compounds from other PAH, their mutagenic activity (Ames Fluctuation test) and dioxin-like activity (EROD activity) were studied. Both, mutation induction factor (up to 2.9±2.7) and dioxin-like activity (Bio-TEQ of 224±75pg/g; represents the amount (pg) 2,3,7,8-tetrachlorodibenzo-p-dioxin per g coal that would provoke the same toxic effect) were rather low. Bioavailability estimated by the bioaccumulation test with Lumbriculus variegatus was also very limited. Based on the obtained results, the environmental risk of the highly abundant alkylated chrysenes and picenes in lignites is concluded to be low.