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Biofilm in drinking water systems is undesirable. Free chlorine and monochloramine are commonly used as secondary drinking water disinfectants, but monochloramine is perceived to penetrate biofilm better than free chlorine. However, this hypothesis remains unconfirmed by direct biofilm monochloramine measurement. This study compared free chlorine and monochloramine biofilm penetration into an undefined mixed-culture nitrifying biofilm by use of microelectrodes and assessed the subsequent effect on biofilm activity and viability by use of dissolved oxygen (DO) microelectrodes and confocal laser scanning microscopy (CLSM) with LIVE/DEAD BacLight. For equivalent chlorine concentrations, monochloramine initially penetrated biofilm 170 times faster than free chlorine, and even after subsequent application to a monochloramine penetrated biofilm, free chlorine penetration was limited. DO profiles paralleled monochloramine profiles, providing evidence that either the biofilm was inactivated with monochloramine's penetration or its persistence reduced available substrate (free ammonia). While this research clearly demonstrated monochloramine's greater penetration, this penetration did not necessarily translate to immediate viability loss. Even though free chlorine's penetration was limited compared to that of monochloramine, it more effectively (on a cell membrane integrity basis) inactivated microorganisms near the biofilm surface. Limited free chlorine penetration has implications when converting to free chlorine in full-scale chloraminated systems in response to nitrification episodes.

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The N-nitrosodimethylamine (NDMA) formation pathway in chloraminated drinking water remains unresolved. In pH 7–10 waters amended with 10 μM total dimethylamine and 800 μeq Cl2·L–1 dichloramine (NHCl2), NDMA, nitrous oxide (N2O), dissolved oxygen (DO), NHCl2, and monochloramine (NH2Cl) were kinetically quantified. NHCl2, N2O, and DO profiles indicated that reactive nitrogen species (RNS) formed during NHCl2 decomposition, including nitroxyl/nitroxyl anion (HNO/NO–) and peroxynitrous acid/peroxynitrite anion (ONOOH/ONOO–). Experiments with uric acid (a ONOOH/ONOO– scavenger) implicated ONOOH/ONOO– as a central node for NDMA formation, which were further supported by the concomitant N-nitrodimethylamine formation. A kinetic model accurately simulated NHCl2, NH2Cl, NDMA, and DO concentrations and included (1) the unified model of chloramine chemistry revised with HNO as a direct product of NHCl2 hydrolysis; (2) HNO/NO– then reacting with (i) HNO to form N2O, (ii) DO to form ONOOH/ONOO–, or (iii) NHCl2 or NH2Cl to form nitrogen gas; and (3) NDMA formation via ONOOH/ONOO– or their decomposition products reacting with (i) dimethylamine (DMA) and/or (ii) chlorinated unsymmetrical dimethylhydrazine (UDMH-Cl), the product of NHCl2 and DMA. Overall, updated NHCl2 decomposition pathways are proposed, yielding (1) RNS via and (2) NDMA via .

Monochloramine disinfection kinetics were determined for the pure-culture ammonia-oxidizing bacterium Nitrosomonas europaea (ATCC 19718) by two culture-independent methods, namely, Live/Dead BacLight (LD) and propidium monoazide quantitative PCR (PMA-qPCR). Both methods were first verified with mixtures of heat-killed (nonviable) and non-heat-killed (viable) cells before a series of batch disinfection experiments with stationary-phase cultures (batch grown for 7 days) at pH 8.0, 25°C, and 5, 10, and 20 mg Cl 2 /liter monochloramine. Two data sets were generated based on the viability method used, either (i) LD or (ii) PMA-qPCR. These two data sets were used to estimate kinetic parameters for the delayed Chick-Watson disinfection model through a Bayesian analysis implemented in WinBUGS. This analysis provided parameter estimates of 490 mg Cl 2 -min/liter for the lag coefficient (b) and 1.6 ؋ 10 ؊3 to 4.0 ؋ 10 ؊3 liter/mg Cl 2 -min for the Chick-Watson disinfection rate constant (k). While estimates of b were similar for both data sets, the LD data set resulted in a greater k estimate than that obtained with the PMA-qPCR data set, implying that the PMA-qPCR viability measure was more conservative than LD. For N. europaea, the lag phase was not previously reported for culture-independent methods and may have implications for nitrification in drinking water distribution systems. This is the first published application of a PMA-qPCR method for disinfection kinetic model parameter estimation as well as its application to N. europaea or monochloramine. Ultimately, this PMA-qPCR method will allow evaluation of monochloramine disinfection kinetics for mixed-culture bacteria in drinking water distribution systems.As a result of stage 1 and stage 2 disinfectant and disinfection by-product rules, chloramination for secondary disinfection in the United States is predicted to increase to 57% of all surface and 7% of all groundwater treatment systems (49). A recent survey reported that 30% of the respondents currently chloraminate to maintain distribution system residual, and other recent surveys suggest that between 8 and 12% of drinking water utilities are contemplating a future switch to chloramination (3, 43).Although chloramines are considered weaker disinfectants than chlorine for suspended bacteria, chloramines are perceived as more effective disinfectants for a biofilm (25, 53). As a result of their lower reactivity, chloramines are believed to penetrate a biofilm further and thereby to more effectively disinfect biofilm bacteria with depth than chlorine (53).Chloramination comes with the risk of distribution system nitrification (2, 21, 22). Based on utility surveys, 30 to 63% of utilities practicing chloramination for secondary disinfection experience nitrification episodes (3,21,43,54). Nitrification in drinking water distribution systems is undesirable and may result in water quality degradation (e.g., disinfectant depletion, coliform occurrences, or nitrite/nitrate formation) and subsequent noncompliance with exis...