Virus inactivation in low ozone exposure water reuse applications.

In drinking water applications, an ozone exposure (Ct) based framework has been historically used to validate ozone disinfection. However, significant viral inactivation can be achieved with little to no measurable ozone exposure. Additionally, ozone exposure depends on multiple water quality variables as well as the calculation/ozone measurement method used. In this study, we evaluated alternative ozone monitoring frameworks as well as the impact of water quality variables on ozone decay kinetics and virus/coliform inactivation. Here we show that both change in UV254 absorbance and applied O3:TOC were well correlated with viral inactivation and these frameworks were resilient to changes in water quality. Both increasing temperature (12-30 °C) and pH (5.5-8.4) was shown to significantly increase the ozone decay rate and decreased the resulting ozone exposure by as much as ∼90% in the case of pH. However, due to the increased reaction rate of ozone with viruses at elevated temperature and pH, there was only a minor impact (∼20% in the case of pH) in overall disinfection performance for a given O3:TOC. These frameworks were also considered for variable source water with TOC (5-11 mg/L) and TSS (1.2-5.8 mg/L). Change in UV254 absorbance or applied ozone dose (mg/L) were the strongest indicators of disinfection performance for source waters of variable TOC, however site-specific testing may be needed to apply this framework. Challenge testing with influent nitrite indicated that ozone disinfection performance is significantly impacted (>50% reduction in inactivation) in the presence of nitrite thus enforcing the importance of accounting for this value in the applied ozone dose. Multi-point ozone dissolution was investigated as an alternative ozone application method that may present a benefit with respect to overall disinfection performance especially if nitrite was present. Developing and validating these alternative monitoring frameworks and ozone application methods is imperative in water reuse applications where unnecessary elevated ozone exposure may lead to harmful byproduct formation.

Optimizing Ozone Disinfection in Water Reuse: Controlling Bromate Formation and Enhancing Trace Organic Contaminant Oxidation.

The use of ozone/biofiltration advanced treatment has become more prevalent in recent years, with many utilities seeking an alternative to membrane/RO based treatment for water reuse. Ensuring efficient pathogen reduction while controlling disinfection byproducts and maximizing oxidation of trace organic contaminants remains a major barrier to implementing ozone in reuse applications. Navigating these challenges is imperative in order to allow for the more widespread application of ozonation. Here, we demonstrate the effectiveness of ozone for virus, coliform bacteria, and spore forming bacteria inactivation in unfiltered secondary effluent, all the while controlling the disinfection byproduct bromate. A greater than 6-log reduction of both male specific and somatic coliphages was seen at specific ozone doses as low as 0.75 O3:TOC. This study compared monochloramine and hydrogen peroxide as chemical bromate control measures in high bromide water (Br- = 0.35 ± 0.07 mg/L). On average, monochloramine and hydrogen peroxide resulted in an 80% and 36% decrease of bromate formation, respectively. Neither bromate control method had any appreciable impact on virus or coliform bacteria disinfection by ozone; however, the use of hydrogen peroxide would require a non-Ct disinfection framework. Maintaining ozone residual was shown to be critical for achieving disinfection of more resilient microorganisms, such as spore forming bacteria. While extremely effective at controlling bromate, monochloramine was shown to inhibit TrOC oxidation, whereas hydrogen peroxide enhanced TrOC oxidation.

Critical Review on Bromate Formation during Ozonation and Control Options for Its Minimization.

Ozone is a commonly applied disinfectant and oxidant in drinking water and has more recently been implemented for enhanced municipal wastewater treatment for potable reuse and ecosystem protection. One drawback is the potential formation of bromate, a possible human carcinogen with a strict drinking water standard of 10 µg/L. The formation of bromate from bromide during ozonation is complex and involves reactions with both ozone and secondary oxidants formed from ozone decomposition, i.e., hydroxyl radical. The underlying mechanism has been elucidated over the past several decades, and the extent of many parallel reactions occurring with either ozone or hydroxyl radicals depends strongly on the concentration, type of dissolved organic matter (DOM), and carbonate. On the basis of mechanistic considerations, several approaches minimizing bromate formation during ozonation can be applied. Removal of bromate after ozonation is less feasible. We recommend that bromate control strategies be prioritized in the following order: (1) control bromide discharge at the source and ensure optimal ozone mass-transfer design to minimize bromate formation, (2) minimize bromate formation during ozonation by chemical control strategies, such as ammonium with or without chlorine addition or hydrogen peroxide addition, which interfere with specific bromate formation steps and/or mask bromide, (3) implement a pretreatment strategy to reduce bromide and/or DOM prior to ozonation, and (4) assess the suitability of ozonation altogether or utilize a downstream treatment process that may already be in place, such as reverse osmosis, for post-ozone bromate abatement. A one-size-fits-all approach to bromate control does not exist, and treatment objectives, such as disinfection and micropollutant abatement, must also be considered.

Ozone disinfection of waterborne pathogens and their surrogates: A critical review.

Viruses, Giardia cysts, and Cryptosporidium parvum oocysts are all major causes of waterborne diseases that can be uniquely challenging in terms of inactivation/removal during water and wastewater treatment and water reuse. Ozone is a strong disinfectant that has been both studied and utilized in water treatment for more than a century. Despite the wealth of data examining ozone disinfection, direct comparison of results from different studies is challenging due to the complexity of aqueous ozone chemistry and the variety of the applied approaches. In this systematic review, an analysis of the available ozone disinfection data for viruses, Giardia cysts, and C. parvum oocysts, along with their corresponding surrogates, was performed. It was based on studies implementing procedures which produce reliable and comparable datasets. Datasets were compiled and compared with the current USEPA Ct models for ozone. Additionally, the use of non-pathogenic surrogate organisms for prediction of pathogen inactivation during ozone disinfection was evaluated. Based on second-order inactivation rate constants, it was determined that the inactivation efficiency of ozone decreases in the following order: Viruses >> Giardia cysts > C. parvum oocysts. The USEPA Ct models were found to be accurate to conservative in predicting inactivation of C. parvum oocysts and viruses, respectively, however they overestimate inactivation of Giardia cysts at ozone Ct values greater than ∼1 mg min L-1. Common surrogates of these pathogens, such as MS2 bacteriophage and Bacillus subtilis spores, were found to exhibit different inactivation kinetics to mammalian viruses and C. parvum oocysts, respectively. The compilation of data highlights the need for further studies on disinfection kinetics and inactivation mechanisms by ozone to better fit inactivation models as well as for proper selection of surrogate organisms.

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 10 µg/L using preformed monochloramine and preoxidation with free chlorine. N-nitrosodimethylamine (NDMA) was formed at an average concentration of 53 ng/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 3-5 mg/L. NDMA was formed at an average concentration of 53 ng/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.