The combustion of fossil fuels give rise to toxic byproducts which pollute our environment and represent potential hazards to human health. Ionizing radiation from nuclear power plants, radioactive waste dumps, and radon in homes pose yet other environmental health hazards. This project is concerned with the mechanisms by which polynuclear aromatic (PNA) compounds on the one hand, and ionizing radiation on the other, ' cause damage to DNA, the genetic material of the cell. The PNA compounds constitute an important class of environmental pollutants derived from energy-related sources which, upon metabolic activation to diolepoxide derivatives, bind covalently to DNA. These bulky PNA-DNA lesions interfere with the normal DNA replication and transcription processes, and give rise to mutations and the initiation of tumors. Chiral and other stereochemical effects play a key role in determining the biological effects of a given PNA diol epoxide and the potentially mutagenic lesions which are formed. In this project, important breakthroughs have been made by devising new and efficient methods for synthesizing stereochemically pure and precisely positioned PNA diol epoxide-DNA lesions in small DNA fragments : (oligonucleotides). In conjunction with several key collaborators, we have elucidated, for the first time, the structures of three stereoisomeric benzo[a]pyrene diol epoxide-DNA adducts. b The manifestations of these adducts on DNA polymerase fidelity, transcription, and DNA repair are currently being investigated for detailed structure-biological activity correlations. Spectroscopic techniques such as circular dichroism, fluorescence, and photoionization play an important role in the characterizations of the PNA adducts. In this connection, a new method was developed for measuring the lifetimes as well as the energies of short-lived (picosecond duration) electronically excited states (a patent application has been filed). Using this technique, it is proposed that short-lived (15 ps) charge-transfer (CT) states in the PNA compound tetracene are activated by a short (20 ps) laser pulse; an unusual extemal photoemission echo due to the recombination of CT states is observed 85 ps after the pulse. The results obtained by this method are relevant to an understanding of the mechanisms of interaction of ionizing radiation with matter.