Making chlorine greener: investigation of alternatives to sulfite for dechlorination

Inorganic and organic chloramines pose a threat to aquatic ecosystems that are exposed to discharges of treated and disinfected wastewater. Conventionally practiced dechlorination with sulfite reduces the most refractory organic chloramines too slowly to produce wastewater effluents that meet current ecosystem protection criteria in the United States (i.e. total residual chlorine ≤ 0.011 mg Cl2/L in freshwaters). Seeking faster dechlorinating agents, we have measured the rates that four test chloramines (NH2CI, N-Cl-piperidine, N-Cl-leucylalanine and N-Cl-alanylalanine) react with 10 selected reducing agents at pH 7.4 and pH 8.4. The aqueous-phase reducing agents that offer speed advantages over sulfite alone include dithionite, thiosulfate, and iodide-mediated sulfite. Ascorbic acid was the most reactive of the sulfur-free agents but was found to be slow relative to sulfite. The potential biological oxygen demand might constrain the choice of aqueous reductants. Metallic iron is shown to reduce inorganic and organic chloramines effectively. The implications of these results for wastewater chlorine reduction and analysis are discussed.