In the present study we have shown that erythrocyte-catalyzed 1,8-dinitropyrene reduction occurs via formation of reactive intermediate species, which bind covalently to haemoglobin and other erythrocyte proteins. In fact after mild-acid hydrolysis of lysate proteins exposed to DNP, the reduced metabolites, 1-amino-8-nitropyrene and 1,8-diaminopyrene, were released, thus indicating the formation of sulphinamide adducts to proteins. These results suggest that haemoglobin adduct biomonitoring would be a useful method of controlling exposure to nitroarene in persons at risk.