Many pharmaceutical compounds and metabolites are being found in surface and ground waters, indicating their ineffective removal by conventional wastewater treatment technologies. Advanced oxidation/reduction processes (AO/RPs), which utilize free-radical reactions to directly degrade chemical contaminants, are alternatives to traditional water treatment. This study reports the absolute rate constants for reaction of three beta-lactam antibiotics (penicillin G, penicillin V, amoxicillin) and a model compound (+)-6-aminopenicillanic acid with the two major AO/RP reactive species: hydroxyl radical ((*)OH) and hydrated electron (e(-)aq). The bimolecular reaction rate constants (M(-1) s(-1)) for penicillin G, penicillin V, amoxicillin, and (+)-6-aminopenicillanic acid for (*)OH were (7.97 +/- 0.11) x 10(9), (8.76 +/- 0.28) x 10(9), (6.94 +/- 0.44) x 10(9), and (2.40 +/- 0.05) x 10(9) and for e(-)aq were (3.92 +/- 0.10) x 10(9), (5.76 +/- 0.24) x 10(9), (3.47 +/- 0.07) x 10(9), and (3.35 +/- 0.06) x 10(9), respectively. To provide a better understanding of the decomposition of the intermediate radicals produced by hydroxyl radical reactions, transient absorption spectra were observed from 1 to 100 micros. In addition, preliminary degradation mechanisms and major products were elucidated using (137)Cs gamma irradiation and LC-MS. These data are required for both evaluating the potential use of AO/RPs for the destruction of these compounds and studies of their fate and transport in surface waters where radical chemistry may be important in assessing their lifetime.