Matrix-assisted laser desorption/ionization (MALDI) and time-of-flight mass spectrometry (TOFMS) are tested for the determination of arylamide adducts of deoxyguanosine. Fifteen matrices were tested for the sensitive determination of N-(guanosin-8-yl)-2-acetylaminofluorene, (dG-C8-AAF), a compound whose structure is representative of carcinogen-DNA adducts formed by nitroaromatic and arylamine carcinogens. Eight matrices allow adduct detection when 560fmole or less is introduced into the TOFMS. Two matrices, α-cyano-4-hydroxycinnamic acid (CHCA) and mercaptobenzothiazole (MBT), promoted adduct detection when 56fmol or less of adduct is introduced into the TOFMS. The other seven matrices did not permit dG-C8-AAF adduct detection at the low pmol level. In all determinations the limit of detection (LOD) is based on the nucleic acid-arylamide, BH + 2 fragment ion formed by the cleavage of the glycosidic bond. The relation between matrix structure and the mechanism of analyte ionization is discussed as well.