Monochloramine Cometabolism by Mixed-Culture Nitrifiers under Drinking Water Conditions

Chloramines are the second most used secondary disinfectant by United States water utilities. However, chloramination may promote nitrifying bacteria. Recently, monochloramine cometabolism by the pure culture ammonia-oxidizing bacteria, <i>Nitrosomonas europaea</i>, was shown to increase monochloramine demand. The current research investigated monochloramine cometabolism by nitrifying mixed cultures grown under more relevant drinking water conditions and harvested from sand-packed reactors before conducting suspended growth batch kinetic experiments. Four types of batch kinetic experiments were conducted: (1) positive controls to estimate ammonia kinetic parameters, (2) negative controls to account for biomass reactivity, (3) utilization associated product (UAP) controls to account for UAP reactivity, and (4) cometabolism experiments to estimate cometabolism kinetic parameters. Kinetic parameters were estimated in AQUASIM with a simultaneous fit to the experimental data. Cometabolism kinetics were best described by a first-order model. Monochloramine cometabolism kinetics were similar to those of ammonia metabolism, and monochloramine cometabolism accounted for 30% of the observed monochloramine loss. These results demonstrated that monochloramine cometabolism occurred in mixed cultures similar to those found in drinking water distribution systems; therefore, monochloramine cometabolism may be a significant contribution to monochloramine loss during nitrification episodes in drinking water distribution systems

Bromamine Decomposition Revisited: A Holistic Approach for Analyzing Acid and Base Catalysis Kinetics

Chloramine chemistry is complex, with a variety of reactions occurring in series and parallel and many that are acid or base catalyzed, resulting in numerous rate constants. Bromide presence increases system complexity even further with possible bromamine and bromochloramine formation. Therefore, techniques for parameter estimation must address this complexity through thoughtful experimental design and robust data analysis approaches. The current research outlines a rational basis for constrained data fitting using Brønsted theory, application of the microscopic reversibility principle to reversible acid or base catalyzed reactions, and characterization of the relative significance of parallel reactions using fictive product tracking. This holistic approach was used on a comprehensive and well-documented data set for bromamine decomposition, allowing new interpretations of existing data by revealing that a previously published reaction scheme was not robust; it was not able to describe monobromamine or dibromamine decay outside of the conditions for which it was calibrated. The current research’s simplified model (3 reactions, 17 constants) represented the experimental data better than the previously published model (4 reactions, 28 constants). A final model evaluation was conducted based on representative drinking water conditions to determine a minimal model (3 reactions, 8 constants) applicable for drinking water conditions

Calibration Curve Raw Data.xlsx

In this research PTR-ToF-MS was used to measure the concentration of five haloamines (monochloramine, dichloramine, monobromamine, dibromamine, and bromochloramine) in aqueous standards and during kinetic experiments that simulate drinking water disinfection. Gas phase sampling was performed and correlated to aqueous concentrations.</p