Although the importance of natural organic matter (NOM) in the environment and in drinking water treatment is well-known, its structure is still ill-defined. The fragmentation patterns of NOM treated by irradiation (various wavelengths--185-400 nm), hydroxyl radicals, chlorine, ozone, and breakdown by a white rot fungus were studied to investigate the structure of chromophoric NOM molecules. Size exclusion chromatography was used to monitor the size distributions of NOM in two natural water waters and two NOM isolates. Three distinct fragmentation patterns were observed: ozone attack appeared to be nonsize specific, UV (> or = 254 nm) irradiation preferentially removed higher molecular weight chromophores, while processes involving hydroxyl radical showed intermediate size specificity. For the samples studied, the UV (> or = 254 nm) irradiation-induced fragmentation of NOM followed the patterns suggested by a simple trimer depolymerization model, supporting the viewpoint that NOM has repeating structural units joined by photolabile chemical bonds. The largest molecules reacted most rapidly, progressively fragmenting into slower reacting smaller molecules, which initially accumulated before breaking down to become nonchromophoric. This dependency of rate on molecular size appears to follow from the law of photochemistry which states the rate of reaction is proportional to the rate of light absorption: larger chromophores had higher molar absorptivities, absorbed more photons, and hence reacted faster than smaller chromophores.