The impacts of bromide concentration and natural organic matter (NOM) characteristics on the formation and speciation of disinfection by-products (DBPs) in chlorinated NOM fractions were investigated. A total of 20 bulk water NOM fractions with a wide range of specific ultraviolet (UV) absorbance (SUVA(254)) values were obtained from a source water employing XAD-8 or XAD-4 resin adsorption in completely mixed batch reactors. SUVA was not a good predictor of DBP [trihalomethanes (THMs), haloacetic acids (HAAs), and adsorbable organic halogens (AOX)] formation and speciation. The destruction in the UV(254) absorbance from chlorination did not correlate with DBP formation at any bromide level. NOM moieties which do not absorb UV light at 254 nm significantly contributed to DBP formation. Mass balance calculations on halogens using THMs, HAAs, and AOX data indicated that significant amounts of DBPs (> 54% of AOX) other than THMs and HAAs were formed in NOM fractions with 60-110 mu g/L bromide concentration. The relative occurrence of such other halogenated by-products decreased with increasing bromide concentrations up to 500 mu g/L level. NOM in the studied water was more susceptible to the formation of brominated THM species as opposed to brominated HAAs. At constant dissolved organic carbon concentration, chlorine dose and pH, increasing bromide concentrations in NOM fractions increased the total concentrations of DBPs and resulted in a shift toward the formation of brominated species. Further, increasing bromide concentrations increased the spectrum of detected species (i.e., occurrence of all nine HAAs) and provided a competitive advantage to THM and HAA precursors in NOM over precursors of other DBPs.