HOBr, formed via oxidation of bromide by free available chlorine (FAC), is frequently assumed to be the sole species responsible for generating brominated disinfection byproducts (DBPs). Our studies reveal that BrCl, Br-2, BrOCl, and Br2O can also serve as brominating agents of the herbicide dimethenamid in -8 solutions of bromide to which FAC was added. Conditions affecting bromine speciation (pH, total free bromine concentration (HOBr), [Cl-], and FAC) were systematically varied, and rates of dimethenamid bromination were measured. Reaction orders in HOBr ranged from 1.09 (+/-0.17) to 1.67 (+/-0.16), reaching a maximum near the pK(a) of HOBr. This complex dependence on HOBr implicates Br2O as an active brominating agent. That bromination rates increased with increasing [Cl-], PAC (at constant HOBr), and excess bromide (where Br->FAC) implicate BrCl, BrOCl, and Br-2, respectively, as brominating agents. As equilibrium constants for the formation of Br2O and BrOCl (aq) have not been previously reported, we have calculated these values (and their gas-phase analogues) using benchmark-quality quantum chemical methods [CCSD(T) up to CCSDTQ calculations plus solvation effects]. The results allow us to compute bromine speciation and hence second-order rate constants. Intrinsic brominating reactivity increased in the order: HOBr << Br2O < BrOCl approximate to Br-2 < BrCl. Our results indicate that species other than HOBr can influence bromination rates under conditions typical of drinking water and wastewater chlorination.