A method of determining a disinfectant composition of a municipal water supply from a water sample that includes: (a) obtaining a water sample from a water source at a sampling location; (b) adding a chlorine-containing material to the water sample in the presence of an oxidation reduction potential (ORP) measurement device; (c) generating a plurality of ORP measurements during addition of the chlorine-containing material to the water sample; (d) estimating a concentration of one or more of free ammonia, fully combined ammonia, monochloramine, or a mixture of dichloramine and trichloramine in the water sample in which the estimation is derived from the relationship between the added chlorine material and the plurality of ORP measurements; and (e) determining a disinfectant composition of the water source at the water sampling location from the concentration calculation. A method of determining free ammonia composition is also included.