Preformed Monochloramine Research Articles

Effectiveness of monochloramine for inactivation of coronavirus in reclaimed water

Fecal shedding of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) by infected persons into wastewater was documented early during the COVID-19 pandemic, thereby stimulating inquiries into the effectiveness of municipal wastewater treatment processes for the reduction of infectious viruses. In wastewater treatment plants, free chlorine has traditionally been the disinfectant utilized due to its low cost and high efficacy. However, regulations limiting disinfection by-products have prompted a shift to chloramination in many areas of the United States. While studies regarding the effectiveness of free chlorine against many viral agents are abundant, the efficacy of monochloramine (NH2Cl) has been less well researched. This study aimed to determine the effectiveness of pre-formed monochloramine for disinfection of human coronavirus 229E (HCoV-229E) in both phosphate-buffered saline (PBS) and reclaimed water from a water reclamation plant in Tucson, Arizona. Reclaimed water was sampled over the course of six months (August 2020 to November 2020), and dosed with monochloramine at 3 mg/L. An additional 1 mg/L free ammonia was added to simulate the operational conditions of the treatment plant. Viability was determined using MRC-5 host cell monolayers, using the TCID50 assay method. An average Ct99.9 (concentration of disinfectant multiplied by the contact time to achieve a 99.9 % reduction of the target organism) of 176 mg*min/L monochloramine was determined. No significant difference in inactivation rate was observed between the dosed reclaimed water and phosphate buffered saline (PBS). These data indicate that monochloramine is an effective disinfectant for coronaviruses. They also indicate that the water matrix type did not significantly impact the disinfection efficacy of monochloramine against HCoV-229E in reclaimed wastewater compared to PBS.

Evaluation of Preformed Monochloramine Reactivity with Processed Natural Organic Matter and Scaling Methodology Development for Concentrated Waters.

To evaluate natural organic matter (NOM) processing impacts on preformed monochloramine (PM) reactivity and as a first step in creating concentrated disinfection byproduct (DBP) mixtures from PM, a rational methodology was developed to proportionally scale PM NOM-related demand in unconcentrated source waters to waters with concentrated NOM. Multiple NOM preparations were evaluated, including a liquid concentrate and reconstituted lyophilized solid material. Published kinetic models were evaluated and used to develop a focused reaction scheme (FRS) that was relatively simple to implement and focused on monochloramine loss, including considerations for inorganic chloramine stability (i.e., autodecomposition) and bromide and iodide impacts. The FRS included critical reaction pathways and accurately simulated (without modification) monochloramine experimental data with and without bromide and iodide present over a range of PM-dosed NOM-free waters. For NOM-containing waters, addition of two NOM reactions in the FRS allowed (i) apportioning monochloramine loss to either inorganic or NOM-related reactions and (ii) selecting experiment conditions to provide an equivalent monochloramine NOM-related demand in unconcentrated and concentrated waters. The methodology provides a framework for future experimentation to evaluate DBP scaling and their speciation in concentrated water matrices when providing an equivalent NOM-related monochloramine demand in unconcentrated and concentrated matrices.

Evaluation of preformed monochloramine for bromate control in ozonation for potable reuse

Bromate, a regulated disinfection byproduct, forms during the ozonation of bromide through reactions with both ozone and hydroxyl radical. In this study, preformed monochloramine was evaluated for use as a bromate suppression method in pilot testing of wastewater reuse with an average bromide concentration of 422±20 µg/L. A dose of 3 mg/L NH2Cl-Cl2 decreased bromate formation by an average of 82% and was sufficient to keep bromate below the MCL at ozone doses up to 8.6 mg/L (1.2 O3:TOC). Removal of 1,4-dioxane through ozonation decreased with increasing NH2Cl dose, confirming that monochloramine suppresses bromate formation, at least in part, by acting as a hydroxyl radical scavenger. This may negatively impact oxidation objectives of ozonation in reuse applications. Increasing monochloramine contact time did not improve bromate suppression, indicating that monochloramine probably did not mask bromide as NHBrCl or other haloamines prior to ozonation. However, NHBrCl and NH2Br may be formed from reactions between HOBr and NH2Cl and excess free ammonia during ozonation. NDMA was formed by ozonation at concentrations up to 79 ng/L and was not enhanced by NH2Cl addition.

Demonstration-scale evaluation of ozone-biofiltration-granular activated carbon advanced water treatment for managed aquifer recharge.

The Sustainable Water Initiative for Tomorrow (SWIFT) program is the effort of the Hampton Roads Sanitation District to implement indirect potable reuse to recharge the depleted Potomac Aquifer. This initiative is being demonstrated at the 1-MGD SWIFT Research Center with a treatment train including coagulation/flocculation/sedimentation (floc/sed), ozonation, biofiltration (BAF), granular activated carbon (GAC) adsorption, and UV disinfection, followed by managed aquifer recharge. Bulk total organic carbon (TOC) removal occurred via multiple treatment barriers including, floc/sed (26% removal), ozone/BAF (30% removal), and adsorption by GAC. BAF acclimation was observed during the first months of plant operation which coincided with the establishment of biological nitrification and dissolved metal removal. Bromate formation during ozonation was efficiently controlled below 10µg/L using preformed monochloramine and preoxidation with free chlorine. N-nitrosodimethylamine (NDMA) was formed at an average concentration of 53ng/L post-ozonation and was removed >70% by the BAFs after several months of operation. Contaminants of emerging concern were removed by multiple treatment barriers including oxidation, biological degradation, and adsorption. The breakthrough of these contaminants and bulk TOC will likely determine the replacement interval of GAC. The ozone/BAC/GAC treatment process was shown to meet all defined treatment goals for managed aquifer recharge. PRACTITIONER POINTS: Floc/sed, biofiltration, and GAC adsorption provide important barriers in carbon-based treatment trains for bulk TOC and trace organic contaminant removal. Biofilter acclimation was observed during the first three months of operation in each operating period as evidenced by the establishment of nitrification. Bromate was effectively controlled during ozonation of a high bromide water with monochloramine doses of 3-5mg/L. NDMA was formed at an average concentration of 53ng/L by ozonation and complete removal was achieved by BAFs after several months of biological acclimation. An average 25% removal of 1,4-dioxane was achieved via oxidation by hydroxyl radicals during ozonation.

Alternative application of preformed monochloramine as a drinking water disinfectant for redosing in long drinking water distribution system servicing remote locations

Chloramine is the disinfectant of choice for long drinking water distribution systems since it is more stable than chlorine, therefore providing a longer lasting disinfectant residual and producing less disinfection byproducts. However, to deliver safe drinking water in remote areas, redosing stations are used where (mostly) chlorine is added to the water to re-establish a disinfectant residual. In this study, the use of a highly concentrated preformed monochloramine solution instead of chlorine for redosing in tanks or reservoirs along extensive distribution systems was investigated. This will avoid unwanted reactions due to chlorine reactivity (formation of disinfection byproducts) and increase the disinfectant stability. Highly concentrated monochloramine solutions (15 mM, 1 gCl2 L−1) are most stable at high pH (10) and low temperature. It was found that the current kinetic model used for drinking water application was not accurate for highly concentrated monochloramine. A simplified kinetic model was developed and successfully used to predict monochloramine stability in our conditions. This will assist water utilities for application of preformed concentrated monochloramine allowing monochloramine redosing in long drinking water distribution systems. Hydrazine, a compound of health concern, might form at high monochloramine concentrations and high pH and needs to be carefully controlled.

N-Nitrosamine formation from chloramination of two common ionic liquids

Ionic liquids (ILs) are a class of solvents increasingly used as “green chemicals.” Widespread applications of ILs have led to concerns about their accidental entry to the environment. ILs have been assessed for some environmental impacts; however, little has been done to characterize their potential impacts on drinking water if ILs accidentally enter surface water. IL cations are often aromatic or alkyl quaternary amines that resemble structures of previously confirmed N-nitrosamine (NA) precursors. Therefore, this study has evaluated two common ILs, 1-ethyl-3-methylimidazolium bromide (EMImBr) and 1-ethyl-1-methylpyrrolidinium bromide (EMPyrBr), for their NA formation potential. Each IL species was reacted with pre-formed monochloramine under various laboratory conditions. The reaction mixtures were extracted using liquid–liquid extraction and analyzed for NAs using high performance liquid chromatography tandem mass spectrometry. At low concentration of IL (250 μmol/L), the yields of NAs (NMEA or NPyr) increased with increasing doses of monochloramine from both IL species. The total NA yield was as high as 2.5 ± 0.3 ng/mg from EMImBr, and as high as 8.6 ± 0.8 ng/mg from EMPyrBr. At high concentration of IL (5 mmol/L), the NA yield reached a maximum at 2.5 mmol/L NH2Cl, and then decreased with subsequent increases in the reactant concentrations, demonstrating ILs' solvent effects. This study re-emphasizes the importance of preventing discharge of ILs to water bodies to prevent secondary impacts on drinking water.

Removal of disinfection byproduct precursors and reduction in additive toxicity of chlorinated and chloraminated waters by ozonation and up-flow biological activated carbon process

The variations of disinfection byproduct (DBP) precursors and DBPs-associated toxic potencies were evaluated by ozonation, followed by a up-flow biological activated carbon (O3/UBAC) filter treating two reconstituted water samples, featuring either high bromide (105.3 μg/L) or dissolved organic nitrogen (0.73 mg N/L) concentration, respectively. Ozonation contributed to ∼20% decrease in dissolved organic carbon (DOC) concentration at a dosage of 0.7 mg of O3/mg of DOC, but no further reduction in DOC level was observed with an increased dose of 1.0 mg of O3/mg of DOC. When chlorine or preformed monochloramine was used as a disinfectant, UBAC process led to ∼40% reduction in the sum of detected DBP formation potential (FP) due to the removal of precursors at a feasible empty bed contact time of 15 min. The integrated effect of ozonation and UBAC biofiltration decreased the sum of DBP FP by ∼50% including halonitromethanes (THNMs), N-nitrosamines (NAs), and bromate, which increased in the effluent of ozonation. Chloramination produced less DBPs by weight as well as DBPs-associated additive toxic potencies than chlorination. The reduction in additive toxic potencies was generally lower than the removal efficiency of DBP FP after chlor(am)ination of treated waters by O3/UBAC, indicating that the removal of DBPs-associated additive toxic potencies should be focused to better understand on the residual risk to public health in controlling DBP precursors.

Formation and speciation of haloacetamides and haloacetonitriles for chlorination, chloramination, and chlorination followed by chloramination

The formation of haloacetamides (HAcAms) and haloacetonitriles (HANs) from a solution containing natural organic matter and a secondary effluent sample was evaluated for disinfection by chlorination, chloramination, and chlorination followed by chloramination (Cl2NH2Cl process). The use of preformed monochloramine (NH2Cl) produced higher concentrations of HAcAms and lower concentrations of HANs than chlorination, while the Cl2NH2Cl process produced the highest concentrations of HAcAms and HANs. These results indicate that the Cl2NH2Cl process, which inhibited the formation of regulated trihalomethanes compared with chlorination, enhanced the formation of HAcAms and HANs. For disinfection in the presence of bromide, brominated dihaloacetamides and dihaloacetonitriles were formed, and the trends were similar to those observed for chlorinated species in the absence of bromide. The degrees of bromine substitution of dihaloacetamides and dihaloacetonitriles were highest for chlorination, followed by the Cl2NH2Cl process and then by the NH2Cl process. For the Cl2NH2Cl process, HAN formation kept gradually increasing with prechlorination time increasing from 0 to 120 min, while HAcAm formation increased only until it reached a maximum at around 10–30 min. These results suggest that the prechlorination time could be reduced to control the formation of HAcAms and HANs. During chloramination, the formation of HAcAms and HANs was lower when using preformed NH2Cl than when chloramines were formed in situ, with higher formation of HAcAms and HANs when chlorine was added before ammonia than vice versa for the secondary effluent; this finding suggests that preformed NH2Cl could be used to inhibit the formation of HAcAms and HANs during chloramination.

Control of nitrosamines during non-potable and de facto wastewater reuse with medium pressure ultraviolet light and preformed monochloramine

Medium pressure UV light and preformed monochloramine can effectively control NDMA formation for de facto or non-potable wastewater reuse.

Disinfection by-product formation from the chlorination and chloramination of amines

This study investigated the relative effect of chlorination and chloramination on DBP formation from seven model amine precursor compounds, representative of those commonly found in natural waters, at pH 6, 7 and 8. The quantified DBPs included chloroform, dichloroacetonitrile (DCAN), trichloroacetonitrile (TCAN) and chloropicrin (trichloronitromethane). The aggregate formation (i.e. the mass sum of the formation from the individual precursors) of chloroform, DCAN and TCAN from all precursors was reduced by respectively 75–87%, 66–90% and 89–93% when considering pre-formed monochloramine compared to chlorine. The formation of both haloacetonitriles decreased with increasing pH following chlorination, but formation after chloramination was relatively insensitive to pH change. The highest formation of chloropicrin was from chloramination at pH 7. These results indicate that, while chloramination is effective at reducing the concentrations of trihalomethanes and haloacetonitriles in drinking water compared with chlorination, the opposite is true for the halonitromethanes.

Factors affecting the formation of disinfection by-products during chlorination and chloramination of secondary effluent for the production of high quality recycled water

During the production of high quality recycled water by reverse osmosis membrane filtration secondary effluent must be disinfected to limit biofouling on the membrane surface. Advanced Water Treatment Plants in South East Queensland, Australia use disinfectant contact times ranging from 30 min up to 24 h. Disinfectants such as chlorine and chloramines react with effluent organic matter to generate disinfection by-products (DBPs) which could be potentially hazardous to human health if the water is destined for supplementing public water supplies. In this context, secondary effluents are of concern because of their high total organic carbon content which can act as DBP precursors. Also, effluent organic matter may form different DBPs to those formed from natural organic matter during conventional drinking water treatment, either in quantity, identity or simply in the abundance of different DBPs relative to each other. It cannot be assumed per se with certainty that DBP formation will be affected in the same way by operational changes as in drinking water production.Response surface modelling has been employed in this study at the bench scale to investigate the effect of reaction time (0–24 h), pH (5.5–8.5), temperature (23–35 °C), disinfection strategy (chlorine vs chloramines used prior to membrane treatment) and the interaction between these different parameters on DBP formation during disinfection of secondary effluent.The concentration of halogenated DBPs formed during the first 24 h of reaction with the different disinfectants followed the order chlorination >> in line-formed monochloramine > pre-formed monochloramine. Contact time with chlorine was the major influencing factor on DBP formation during chlorination, except for the bromine-containing trihalomethanes and dibromoacetonitrile for which pH was more significant. Chlorination at high pH led to an increased formation of chloral hydrate, trichloronitromethane, dibromoacetonitrile and the four trihalomethanes while the opposite effect was observed for the other targeted DBPs. Temperature was identified as the least influencing parameter compared to pH and reaction time for all DBPs in all the disinfection strategies, except for the formation of chloral hydrate where pH and temperature had a similar significance and bromoform that was similarly affected by temperature and reaction time. Chloramines employed at pH 8.5 reduced the concentration of all studied DBPs compared to pH 5.5. Furthermore, reaction time was the most significant factor for trichloronitromethane, chloroform, trichloroacetonitrile, dichloroacetonitrile and bromochloroacetonitrile formation while pH was the most influencing factor affecting the formation of the remaining DBPs.

Impact of Tertiary Treatment Processes on the Effectiveness of Chloramination for Biological Growth Control in Recirculating Cooling Systems Using Treated Municipal Wastewater

Adequate biocide addition is the key to control biological growth-related problems in recirculating cooling systems of thermoelectric power plants. The use of monochloramine (MCA) as the primary biocide is as effective as the use of free-chlorine in cooling systems using secondary-treated municipal wastewater (MWW) as the sole makeup water source. However, severe scaling caused by the secondary effluent necessitates incorporation of an additional treatment of secondary effluent (i.e., tertiary treatment) prior to use as makeup water for recirculating cooling systems. In the research reported in this paper, the effectiveness of MCA as a cooling-system biocide was evaluated for three types of tertiary-treated MWW, as follows: (1) acidification, (2) nitrification and sand filtration, and (3) nitrification, sand filtration, and granular activated-carbon adsorption. The impact of these tertiary treatment processes on chloramination was studied in both laboratory and pilot-scale experiments. For the third type of MWW treatment, reducing the total organic carbon (TOC) content in MWW exerted a 37% decrease in biological growth potential but less than a 5% decrease in biological growth rate. A MCA residual of 2–3 mg/L was required to achieve biological-growth control objectives with respect to planktonic and sessile heterotrophic bacteria in cooling systems regardless of the tertiary treatment employed. Legionella analyses indicated that chloramination was effective in controlling proliferation of these species for all tertiary-treated wastewaters. Overall, preformed MCA was effective as a primary biocide in all tertiary-treated MWW evaluated in the research reported in this paper. Nitrification followed by sand filtration was the optimal tertiary treatment among the three investigated MWW because the biological-control objectives could be achieved with lower doses. The use of granular activated-carbon adsorption revealed no additional benefit compared to nitrification and sand filtration.

Effect of Ammonia and Chloramine Pretreatment during the Ozonation of a Colored Groundwater with Elevated Bromide

Ozone coupled with pre-chloramination was evaluated as an effective color removal and bromate control method for groundwater at Mesa Water's Well #8. A modified solution ozone test procedure was employed to simulate the sidestream ozone injection. Satisfactory color removal (<10 PtCo CU) was achieved with 2 mg/L of ozone in the presence or absence of preformed monochloramine or ammonia. While bromate formation was reduced by 67% and 83% with 0.3 and 0.6 mg/L of ammonia-N alone, respectively, 68% and 92% of bromate formation was suppressed with 1.0 and 2.0 mg/L of monochloramine as Cl2, respectively. Only the pre-treatment with 2.0 mg/L of monochloramine provided sufficient bromate control to meet its maximum contaminant level of 10 μg/L. UV and fluorescence analyses showed effective destruction of color-causing organics by ozone in the presence of preformed monochloramine.

Anion Exchange Resins as a Source of Nitrosamines and Nitrosamine Precursors

Anion exchange resins are important tools for the removal of harmful anionic contaminants from drinking water, but their use has been linked to the presence of carcinogenic nitrosamines in treated drinking water. In bench-scale batch and column experiments, anion exchange resins from a large, representative group were investigated as sources of the nitrosamines N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine (NDEA), N-nitrosodi-n-propylamine (NDPA), and N-nitrosodi-n-butylamine (NDBA) and their precursors. Several resins were found to release high levels (up to >2000 ng/L, orders of magnitude above drinking water regulatory levels) of nitrosamines upon initial rinsing with lab-grade water, with levels subsiding within 50-100 bed volumes of rinsing. Resins released similarly high levels of nitrosamine precursors, with spikes in precursor release triggered by regeneration of resins with sodium chloride or by interruptions in flow resulting in prolonged contact times. Free chlorine or preformed monochloramine in feedwater led to the production of nitrosamines. Resins released different nitrosamines and precursors depending on their functional groups, with some resins releasing as many as three different nitrosamines and their precursors. These findings have significant implications for the pretreatment and appropriate use of anion exchange resins by drinking water utilities and for the production of anion exchange resins by manufacturers.

Control of biological growth in recirculating cooling systems using treated secondary effluent as makeup water with monochloramine

Secondary-treated municipal wastewater, an abundant and widely distributed impaired water source, is a promising alternative water source for thermoelectric power plant cooling. However, excessive biological growth is a major challenge associated with wastewater reuse in cooling systems as it can interfere with normal system operation as well as enhance corrosion and scaling problems. Furthermore, possible emission of biological aerosols (e.g., Legionella pneumophila) with the cooling tower drift can lead to public health concerns within the zone of aerosol deposition. In this study, the effectiveness of pre-formed and in-situ-formed monochloramine was evaluated for its ability to control biological growth in recirculating cooling systems using secondary-treated municipal wastewater as the only makeup water source. Bench-scale studies were compared with pilot-scale studies for their ability to predict system behavior under realistic process conditions. Effectiveness of the continuous addition of pre-formed monochloramine and monochloramine formed in-situ through the reaction of free chlorine with ammonia in the incoming water was evaluated in terms of biocide residual and its ability to control both planktonic and sessile microbial populations. Results revealed that monochloramine can effectively control biofouling in cooling systems employing secondary-treated municipal wastewater and has advantages relative to use of free chlorine, but that bench-scale studies seriously underestimate biocide dose and residual requirements for proper control of biological growth in full-scale systems. Pre-formed monochloramine offered longer residence time and more reliable performance than in-situ-formed monochloramine due to highly variable ammonia concentration in the recirculating water caused by ammonia stripping in the cooling tower. Pilot-scale tests revealed that much lower dosing rate was required to maintain similar total chlorine residual when pre-formed monochloramine was used as compared to in-situ-formed monochloramine. Adjustment of biocide dose to maintain monochloramine residual above 3mg/L is needed to achieve successful biological growth control in recirculating cooling systems using secondary-treated municipal effluent as the only source of makeup water.

The effects of selected preoxidation strategies on I-THM formation and speciation

In this study, the impacts of three preoxidation strategies [i.e., using potassium permanganate (KMnO4), chlorine dioxide (ClO2), or hydrogen peroxide (H2O2)] before preformed monochloramine (NH2Cl) addition on the formation and speciation of iodinated trihalomethanes (I-THMs) were evaluated at the Br−/I− mass ratio of 10 in two natural waters. The effects of preoxidant dose, Br−/DOC, and I−/DOC ratio were investigated. Preoxidation with KMnO4 increased I-THM formation due to an increase in iodoform (CHI3) and brominated I-THM (CHBrClI, CHBrI2, CHBr2I) formation. In contrast, preoxidation with ClO2 sometimes reduced I-THM formation, primarily due to a reduction in CHI3 formation. Preoxidation with H2O2 had no effect on I-THM formation or speciation. I-THM formation from each preoxidant alone was considerably less than the formation from NH2Cl. Overall, preoxidant type, preoxidant/DOC, preoxidant/I−, and I−/DOC ratios are the important factors that water utilities should evaluate when assessing the impact of preoxidation for controlling I-THM formation.

I-THM Formation and Speciation: Preformed Monochloramine versus Prechlorination Followed by Ammonia Addition

An increasing number of utilities in the United States have been switching from chlorination to chloramination practices to comply with the more stringent trihalomethane (THM) and haloacetic acid (HAA) regulations. This has important implications for disinfection byproduct (DBP) formation because the reactions of chlorine and monochloramine (NH(2)Cl) with natural organic matter (NOM) are not the same. In this study, iodinated trihalomethane (I-THM) formation from preformed NH(2)Cl and prechlorination (at two chlorine doses and contact times) followed by ammonia addition was compared. A representative bromide/iodide ratio of 10:1 was selected and four bromide/iodide levels (ambient, 50/5 or 100/10, 200/20, and 800/80 [μg/L/μg/L]) were evaluated. The results showed that I-THM formation was generally lower for prechlorination as compared to preformed NH(2)Cl due to the oxidation of iodide to iodate by chlorine. However, while prechlorination minimized iodoform (CHI(3)) formation, prechlorination sometimes formed more I-THMs as compared to preformed NH(2)Cl due to a large increase in the formation of brominated I-THM species, which were formed at much smaller amounts from preformed NH(2)Cl. I-THM concentrations and speciation for the two chloramination scenarios (i.e., preformed NH(2)Cl vs prechlorination followed by ammonia) depended on chlorine dose, contact time, bromide/iodide concentration, and NOM characteristics of the source water (SUVA(254)).

Understanding the operational parameters affecting NDMA formation at Advanced Water Treatment Plants

N-nitrosodimethylamine (NDMA) can be formed when secondary effluents are disinfected by chloramines. By means of bench scale experiments this paper investigates operational parameters than can help Advanced Water Treatment Plants (AWTPs) to reduce the formation of NDMA during the production of high quality recycled water. The formation of NDMA was monitored during a contact time of 24 h using dimethylamine as NDMA model precursor and secondary effluent from wastewater treatment plants. The three chloramine disinfection strategies tested were pre-formed and in-line formed monochloramine, and pre-formed dichloramine. Although the latter is not employed on purpose in full-scale applications, it has been suggested as the main contributing chemical generating NDMA during chloramination. After 24 h, the NDMA formation decreased in both matrices tested in the order: pre-formed dichloramine > in-line formed monochloramine ≫ pre-formed monochloramine. The most important parameter to consider for the inhibition of NDMA formation was the length of contact time between disinfectant and wastewater. Formation of NDMA was initially inhibited for up to 6 h with concentrations consistently <10 ng/L during these early stages of disinfection, regardless of the disinfection strategy. The reduction of the contact time was implemented in Bundamba AWTP (Queensland, Australia), where NDMA concentrations were reduced by a factor of 20 by optimizing the disinfection strategy.

Effect of some parameters on the formation of chloroform during chloramination of aqueous solutions of resorcinol

The effects of various factors (N/Cl ratio used to prepare monochloramine, monochloramine doses, pH and contact time) on the monochloramine demand and on the chloroform yield during chloramination of resorcinol have been investigated. Chloramination experiments were carried out at 24 ± 1 °C, at pH values ranging from 6.5 to 12 using a bicarbonate/carbonate buffer and preformed monochloramine solutions prepared at pH 8.5 with N/Cl ratios ([NH 4Cl] 0/[Total free Cl 2] 0 ranging from 1.0 to 150 mol/mol). Kinetic experiments ([Resorcinol] 0 = 5 or 100 μM, [NH 2Cl] 0/[Resorcinol] 0 = 20 mol/mol, pH = 8.5 ± 0.1) showed a slow increase of the monochloramine consumption with reaction time. The monochloramine demands after reaction times of 7 days ([Resorcinol] 0 = 100 μM) and 14 days ([Resorcinol] 0 = 5 μM) were equal to 8.5 mol of NH 2Cl/mole of resorcinol and were higher than the chlorine demands (≈7.3 mol/mol). Chloroform yields from monochloramination of resorcinol were lower than 8% (<80 mmol of CHCl 3/mole of resorcinol) and were less than the yields obtained by chlorination (0.9–0.95 mol/mol). Chloroform productions increased with increasing monochloramine dose and reaction time and decreased with increasing pH values within the pH range 6.5–10. Chloroform formation markedly decreased when the N/Cl ratio increased from 1 to 1.5 mol/mol and was suppressed at N/Cl > 100 mol/mol. The data obtained in the present work suggest that free chlorine released from monochloramine hydrolysis plays a significant role on the formation of chloroform during chloramination of resorcinol at N/Cl ratios close to unity (1.0 < N/Cl < 1.5).

Influence of the Method of Reagent Addition on Dichloroacetonitrile Formation during Chloramination

Formation of dichloroacetonitrile (DCAN) in natural waters was evaluated for different disinfection scenarios, including application of free chlorine, preformed monochloramine or dichloramine, or formation of chloramines in situ by addition of free chlorine and ammonia in either order. Formation of DCAN was highest during free chlorination. Regardless of the order of ammonia or chlorine addition, DCAN formation was consistently higher over 1-2 day contact times when chloramines were formed in situ than when preformed chloramines were applied. During in situ chloramine formation, organic amine precursors effectively competed with ammonia to react with free chlorine, forming organic dichloramine intermediates to nitrile formation. Combined with previous research indicating that application of preformed monochloramine reduced nitrosamine formation, the results indicate that application of preformed monochloramine could provide an inexpensive alternative for chloraminating utilities to significantly reduce the exposure to DCAN and nitrosamines for consumers located within 1-2 days of water travel time from the treatment plant. This technique would be applicable in situations where chloramination is used alone (e.g., chlorination of non-nitrified secondary wastewater effluents during municipal wastewater recycling), or combined with primary disinfectants other than free chlorine (e.g., ozonation, chlorine dioxide, or ultraviolet light).