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.

Using total adenosine triphosphate (tATP) measurements for cyanobacterial bloom monitoring and response assessment during algaecide treatments.

Total adenosine triphosphate (tATP) was investigated for its potential as a rapid indicator of cyanobacterial growth and algaecide effectiveness. tATP and other common bloom monitoring parameters were measured over the growth cycles of cyanobacteria and green algae in laboratory cultures and examined at a drinking water source during an active bloom. Strong correlations (R2>0.78) were observed between tATP and chlorophyll-a in cyanobacteria cultures. tATP offered greater sensitivity by increasing two orders of magnitude approximately 7 d before changes in chlorophyll-a or optical density were observed in Lyngbya sp. and Dolichospermum sp. cultures. Increases in tATP per cell coincided with the onset of exponential growth phases in lab cultures and increase in cell abundance in field samples, suggesting that ATP/cell is a sensitive indicator that may be used to identify the development of blooms. Bench-scale trials using samples harvested during a bloom showed that tATP exhibited a clear dose-response during copper sulfate (CuSO4) and hydrogen peroxide (H2O2) treatment compared to chlorophyll-a and cell counts, indicating that cellular production and storage of ATP decreases even when live and dead cells cannot be distinguished. During Copper (Cu) algaecide application at a reservoir used as a drinking water source, tATP and cell counts decreased following initial algaecide application; however, the bloom rebounded within 10 d showing that the Cu algaecide only has limited effectiveness. In this case, tATP was a sensitive indicator to bloom rebounding after algaecide treatments and correlated positively with cell counts (R2=0.7). These results support the use of tATP as a valuable complementary bloom monitoring tool for drinking water utilities to implement during the monitoring and treatment of cyanobacterial blooms.

Intracellular organic matter from cyanobacteria as a precursor for carbonaceous and nitrogenous disinfection byproducts.

The formation of total organic halogen (TOX), carbonaceous disinfection byproducts (DBPs) (trihalomethanes (THMs) and haloacetic acids (HAAs)), and nitrogenous DBPs (trichloronitromethane (TCNM) or chloropicrin, haloacetonitriles (HANs), and nitrosamines) was examined during the chlorination or chloramination of intracellular organic matter (IOM) extracted from Microcystis aeruginosa, Oscillatoria sp. (OSC), and Lyngbya sp. (LYN). The percentage of unknown TOX (22-38%) during chlorination indicated that the majority of DBPs were identified among THMs, HAAs, TCNM, and HANs. Bromide was readily incorporated into DBPs with speciation shifting slightly from dihalogenated species to trihalogenated species. During formation potential testing with chloramines, nitrosamine yields from IOM were measured for N-nitrosodimethylamine (NDMA, 10-52 ng/mgC), N-nitrosopyrrolidine (NPYR, 14 ng/mgC), N-nitrosopiperidine (NPIP, 3.7-5.5 ng/mgC), and N-nitrosomethylethylamine (NMEA, 2.1-2.6 ng/mgC). When IOM was added to a natural water matrix, the nitrosamine yields were not realized likely due to competition from natural organic matter. Ozonation increased NDMA and NMEA formation and reduced NPYR and NPIP formation during subsequent chloramination. In addition, ozone oxidation of IOM formed detectable concentrations of aldehydes, which may contribute to DBP formation. Finally, bioluminescence-based test results showed that >99% of the IOM extracted from OSC and LYN was biodegradable. Therefore, a biological treatment process could minimize this source of DBP precursor material during drinking water treatment.

Prediction of micropollutant elimination during ozonation of municipal wastewater effluents: use of kinetic and water specific information.

Ozonation is effective in improving the quality of municipal wastewater effluents by eliminating organic micropollutants. Nevertheless, ozone process design is still limited by (i) the large number of structurally diverse micropollutants and (ii) the varying quality of wastewater matrices (especially dissolved organic matter). These issues were addressed by grouping 16 micropollutants according to their ozone and hydroxyl radical ((•)OH) rate constants and normalizing the applied ozone dose to the dissolved organic carbon concentration (i.e., g O3/g DOC). Consistent elimination of micropollutants was observed in 10 secondary municipal wastewater effluents spiked with 16 micropollutants (∼2 µg/L) in the absence of ozone demand exerted by nitrite. The elimination of ozone-refractory micropollutants was well predicted by measuring the (•)OH exposure by the decrease of the probe compound p-chlorobenzoic acid. The average molar (•)OH yields (moles of (•)OH produced per mole of ozone consumed) were 21 ± 3% for g O3/g DOC = 1.0, and the average rate constant for the reaction of (•)OH with effluent organic matter was (2.1 ± 0.6) × 10(4) (mg C/L)(-1) s(-1). On the basis of these results, a DOC-normalized ozone dose, together with the rate constants for the reaction of the selected micropollutants with ozone and (•)OH, and the measurement of the (•)OH exposure are proposed as key parameters for the prediction of the elimination efficiency of micropollutants during ozonation of municipal wastewater effluents with varying water quality.

Design and operational considerations in response to Legionella occurrence in Las Vegas Valley groundwater.

Legionella occurrence monitoring is not required by United States Environmental Protection Agency (USEPA) drinking water regulations, and few occurrence studies exist for Legionella in source water or distribution systems. Legionella occurrence was monitored in Las Vegas Valley (Las Vegas, Nevada, USA) drinking water sources, including non-treated surface water, seasonal groundwater (61 wells, before and after chlorination), finished water (after treatment at water treatment facilities), and chlorinated distribution system water (at 9 reservoirs and 75 sample locations throughout the network). Legionella pneumophila was detected at least once at each of the wells sampled before chlorination, with an overall positivity rate of 38% (343/908). During well start-up (time<2 hours; turbidity>3 NTU), L. pneumophila concentrations averaged 2,792±353 MPN/100 mL, with a median of 105 MPN/100 mL, and range of <1 to 90,490 MPN/100 mL across 61 seasonally operated (typically April-October) groundwater wells. After initial flushing (turbidity<3 NTU), the average concentration decreased by more than two orders of magnitude to 24±3 MPN/100 mL but ranged from <1 to >2,273 MPN/100 mL. This trend indicates that stagnation (up to 391 days) contributed to greater initial concentrations, and flushing alone was incapable of complete L. pneumophila elimination. L. pneumophila concentration was significantly, positively correlated with total aqueous adenosine triphosphate (ATP) (p<0.00001, r=0.41-0.71), turbidity (p<0.00001, r=0.27-0.51), orthophosphate (p=0.35-0.076, r=0.51-0.59), and pump depth (p=0.032, r=0.40). During a full-scale assessment of chlorination (Ct=0.7 to 10.5 mg-min/L; T=26.6-28.1°C), substantial reduction of Legionella spp. (up to 2.5 logs) was observed; although, detectable concentrations were still measured. Extrapolating from a Chick-Watson model (log inactivation=0.28*(Ct); R2=0.87) constructed from the full-scale chlorination results, 3- and 4-log inactivation in Las Vegas Valley groundwater would require 10.8 and 14.3 mg-min/L, respectively; at least 3-log inactivation was required to bring Legionella spp. to below detection at the studied well. Chlorine exposure (Ct=0.1 to 10.9 mg-min/L) at most wells discharging directly to the distribution system was insufficient to fully inactivate Legionella spp. After discussing these findings with the state regulatory agency, direct-to-distribution wells (38 of 61 wells) remained out of operation; the distribution system, wells, and reservoirs were monitored for Legionella and chlorine residual, and additional treatment scenarios were identified for further evaluation. Legionella was either not detected or was well controlled in surface water, finished effluent from the drinking water treatment plant, chlorinated reservoirs, and the chlorinated distribution system. This study emphasizes the importance of utility-driven, non-regulatory research in order to protect public health and also identifies the need for greater occurrence monitoring and guidance for Legionella in groundwater supplies.

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.

Comparative Assessment of Physical and Chemical Cyanobacteria Cell Lysis Methods for Total Microcystin-LR Analysis.

Standardization and validation of alternative cell lysis methods used for quantifying total cyanotoxins is needed to improve laboratory response time goals for total cyanotoxin analysis. In this study, five cell lysis methods (i.e., probe sonication, microwave, freeze-thaw, chemical lysis with Abraxis QuikLyseTM, and chemical lysis with copper sulfate) were assessed using laboratory-cultured Microcystis aeruginosa (M. aeruginosa) cells. Methods were evaluated for destruction of cells (as determined by optical density of the sample) and recovery of total microcystin-LR (MC-LR) using three M. aeruginosa cell densities (i.e., 1 × 105 cells/mL (low-density), 1 × 106 cells/mL (medium-density), and 1 × 107 cells/mL (high-density)). Of the physical lysis methods, both freeze-thaw (1 to 5 cycles) and pulsed probe sonication (2 to 10 min) resulted in >80% destruction of cells and consistent (>80%) release and recovery of intracellular MC-LR. Microwave (3 to 5 min) did not demonstrate the same decrease in optical density (<50%), although it provided effective release and recovery of >80% intracellular MC-LR. Abraxis QuikLyseTM was similarly effective for intracellular MC-LR recovery across the different M. aeruginosa cell densities. Copper sulfate (up to 500 mg/L Cu2+) did not lyse cells nor release intracellular MC-LR within 20 min. None of the methods appeared to cause degradation of MC-LR. Probe sonication, microwave, and Abraxis QuikLyseTM served as rapid lysis methods (within minutes) with varying associated costs, while freeze-thaw provided a viable, low-cost alternative if time permits.

A critical review on operation and performance of source water control strategies for cyanobacterial blooms: Part I-chemical control methods.

Cyanobacterial blooms produce nuisance metabolites (e.g., cyanotoxins and T&O compounds) thereby posing water quality management issues for aquatic sources used for potable water production, aquaculture, and recreation. A variety of in-lake/reservoir control measures are implemented to reduce the abundance of nuisance cyanobacteria biomass or decrease the amount of available phosphorous (P). This paper critically reviews the chemical control strategies implemented for in-lake/reservoir management of cyanobacterial blooms, i.e., algaecides and nutrient sequestering coagulants/flocculants, by highlighting (i) their mode of action, (ii) cases of successful and unsuccessful treatment, (iii) and factors influencing performance (e.g., water quality, process control techniques, source water characteristics, etc.). Algaecides generally result in immediate improvements in water quality and offer selective cyanobacterial control when peroxide-based alagecides are used. However, they have a range of limitations: causing cell lysis and release of cyanotoxins, posing negative impacts on aquatic plants and animals, leaving behind environmentally relevant treatment residuals (e.g., Cu in water and sediments), and offering only short-term bloom control characterized by cyanobacterial rebound. Coagulants/flocculants (alum, iron, calcium, and lanthanum bentonite) offer long-term internal nutrient control when external nutrient loading is controlled. Treatment performance is often influenced by background water quality conditions, and source water characteristics (e.g., surface area, depth, mixing regimes, and residence time). The reviewed case studies highlight that external nutrient load reduction is the most fundamental aspect of cyanobacterial control. None of the reviewed control strategies provide a comprehensive solution to cyanobacterial blooms.

A critical review on operation and performance of source water control strategies for cyanobacterial blooms: Part II-mechanical and biological control methods.

This review summarizes current knowledge on mechanical (artificial mixing, hypolimnetic aeration, dredging, and sonication) and biological (biomanipulation, macrophytes, and straws) methods for the management of cyanobacterial blooms in drinking water sources. Emphasis has been given to (i) the mechanism of cyanobacterial control, (ii) successful and unsuccessful case studies, and (iii) factors influencing successful implementation. Most mechanical and biological control strategies offer long-term control. However, their application can be cost-prohibitive and treatment efficacy is influenced by source water geometry and continual nutrient inputs from external sources. When artificial mixing and hypolimnetic oxygenation units are optimized based on source water characteristics, observed water quality benefits included increased dissolved oxygen contents, reduced internal loading of nutrients, and lower concentrations of reduced ions . Treatment efficacy during oxygenation and aeration was derailed by excessive sedimentation of organic matter and sediment characteristics such as low Fe/P ratios. Dredging is beneficial for contaminated sediment removal, but it is too costly to be a practical bloom control strategy for most systems. Sonication control methods have contradictory findings requiring further research to evaluate the efficacy and applicability for field-scale control of cyanobacteria. Biological control methods such as biomanipulation offer long-term treatment benefits; however, investigations on the mechanisms of field-scale cyanobacterial control are still limited, particularly with the use of macrophytes and straws. Each control method has site-specific strengths, limitations, and ecological impacts. Reduction of external nutrient inputs should still be a significant focus of restoration efforts as treatment benefits from mechanical and biological control were commonly offset by continued nutrient inputs.

Delayed Release of Intracellular Microcystin Following Partial Oxidation of Cultured and Naturally Occurring Cyanobacteria.

Oxidation processes can provide an effective barrier to eliminate cyanotoxins by damaging cyanobacteria cell membranes, releasing intracellular cyanotoxins, and subsequently oxidizing these toxins (now in extracellular form) based on published reaction kinetics. In this work, cyanobacteria cells from two natural blooms (from the United States and Canada) and a laboratory-cultured Microcystis aeruginosa strain were treated with chlorine, monochloramine, chlorine dioxide, ozone, and potassium permanganate. The release of microcystin was measured immediately after oxidation (t ≤ 20 min), and following oxidant residual quenching (stagnation times = 96 or 168 h). Oxidant exposures (CT) were determined resulting in complete release of intracellular microcystin following chlorine (21 mg-min/L), chloramine (72 mg-min/L), chlorine dioxide (58 mg-min/L), ozone (4.1 mg-min/L), and permanganate (391 mg-min/L). Required oxidant exposures using indigenous cells were greater than lab-cultured Microcystis. Following partial oxidation of cells (oxidant exposures ≤ CT values cited above), additional intracellular microcystin and dissolved organic carbon (DOC) were released while the samples remained stagnant in the absence of an oxidant (>96 h after quenching). The delayed release of microcystin from partially oxidized cells has implications for drinking water treatment as these cells may be retained on a filter surface or in solids and continue to slowly release cyanotoxins and other metabolites into the finished water.

Effect of ozone exposure on the oxidation of trace organic contaminants in wastewater.

Three tertiary-treated wastewater effluents were evaluated to determine the impact of wastewater quality (i.e. effluent organic matter (EfOM), nitrite, and alkalinity) on ozone (O(3)) decomposition and subsequent removal of 31 organic contaminants including endocrine disrupting compounds, pharmaceuticals, and personal care products. The O(3) dose was normalized based upon total organic carbon (TOC) and nitrite to allow comparison between the different wastewaters with respect to O(3) decomposition. EfOM with higher molecular weight components underwent greater transformation, which corresponded to increased O(3) decomposition when compared on a TOC basis. Hydroxyl radical (()OH) exposure, measured by parachlorobenzoic acid (pCBA), showed that limited ()OH was available for contaminant destruction during the initial stage of O(3) decomposition (t<30s) due to the effect of the scavenging by the water quality. Advanced oxidation using O(3) and hydrogen peroxide did not increase the net production of ()OH compared to O(3) under the conditions studied. EfOM reactivity impacted the removal of trace contaminants when evaluated based on the O(3):TOC ratio. Trace contaminants with second order reaction rate constants with O(3)(k(O)(3))>10(5)M(-1)s(-1) and ()OH (k(OH))>10(9)M(-1)s(-1), including carbamazepine, diclofenac, naproxen, sulfamethoxazole, and triclosan, were >95% removed independent of water quality when the O(3) exposure (integralO(3)t) was measurable (0-0.8mgmin/L). O(3) exposure would be a conservative surrogate to assess the removal of trace contaminants that are fast-reacting with O(3). Removal of contaminants with k(O)(3) < 10M(-1)S(-1) , and k(OH)>10(9)M(-1)s(-1), including atrazine, iopromide, diazepam, and ibuprofen, varied when O(3) exposure could not be measured, and appeared to be dependent upon the compound specific k(OH). Atrazine, diazepam, ibuprofen and iopromide provided excellent linear correlation with pCBA (R(2)>0.86) making them good indicators of ()OH availability.

Evaluation of a photocatalytic reactor membrane pilot system for the removal of pharmaceuticals and endocrine disrupting compounds from water.

A photocatalytic reactor membrane pilot system, employing UV/TiO(2) photocatalysis, was evaluated for its ability to remove thirty-two pharmaceuticals, endocrine disrupting compounds, and estrogenic activity from water. Concentrations of all compounds decreased following treatment, and removal followed pseudo-first-order kinetics as a function of the amount of treatment. Twenty-nine of the targeted compounds in addition to total estrogenic activity were greater than 70% removed while only three compounds were less than 50% removed following the highest level of treatment (4.24 kW h/m(3)). No estrogenically active transformation products were formed during treatment. Additionally, the unit was operated in photolytic mode (UV only) and photolytic plus H(2)O(2) mode (UV/H(2)O(2)) to determine the relative amount of energy required. Based on the electrical energy per order (EEO), the unit achieved the greatest efficiency when operated in photolytic plus H(2)O(2) mode for the conditions tested.

Using discrete and online ATP measurements to evaluate regrowth potential following ozonation and (non)biological drinking water treatment.

Water utilities must control microbial regrowth in the distribution system to protect public health. In this study, an adenosine triphosphate (ATP)-based biomass production potential test using indigenous bacterial communities were used to evaluate regrowth potential following ozonation with either biofiltration (BF) or sustained chlorination (SCl2). Two full-scale water treatment plants with different upstream processes (i.e., WTP-BF: ozonation, coagulation/flocculation, biofiltration, UV irradiation, chlorination; and WTP-SCl2: ozonation, chlorination, coagulation/flocculation, filtration, chlorination) were compared. Characterization of indigenous bacteria using 16S rRNA gene sequencing, qPCR, and cellular ATP (cATP) showed microbial diversity changes across treatment, biomass sloughing from biofilters (effluent cATP = 30 ±â€¯1 ng/L), and disinfection by chlorine (cATP < 1 ng/L). For both WTPs, 14-day cumulative biomass production (CBPt =  ∑t=0tATP(t)×Δt) was highest for ozonated water samples (CBP14 = 1.2 × 103-3.0 × 103 d ngATP/L). CBP further increased with increasing ozone dose due to production of more biodegradable carbon. Growth promotion by carbon was confirmed from the consumption of ozonation byproducts (carboxylic acids, aldehydes) and the increase in CBP (9.5 × 102-2.9 × 103 d ngATP/L) after addition of 50-300 µgC/L acetate. Ozone followed by sustained chlorination (WTP-SCl2) effectively controlled biomass growth across the treatment process (CBP14 <10 d ngATP/L). In contrast, ozone followed by biofiltration (WTP-BF) reduced regrowth potential by 30% (biofilter influent CBP14 = 1.3 × 103 d ngATP/L; biofilter effluent CBP14 = 9.3 × 102 d ngATP/L). After adding chlorine to the biofilter effluent, CBP14 was reduced to <10 d ngATP/L. Lastly, online ATP measurements confirmed the discrete measurements and improved identification of the cATP peak and growth phases of indigenous bacteria.

Using rapid quantification of adenosine triphosphate (ATP) as an indicator for early detection and treatment of cyanobacterial blooms.

Early detection of harmful cyanobacterial blooms allows identification of potential risk and appropriate selection of treatment techniques to prevent exposure in recreational water bodies and drinking water supplies. Here, luminescence-based adenosine triphosphate (ATP) analysis was applied to monitor and treat cultured and naturally occurring cyanobacteria cells. When evaluating lab-cultured Microcystis aeruginosa, ATP concentrations (≤252,000 pg/mL) had improved sensitivity and correlated well (R2 = 0.969) with optical density measurements at 730 nm (OD730; ≤0.297 cm-1). Following one year of monitoring of a surface water supply, ATP concentrations (≤2000 pg/mL) correlated (R2 = 0.791) with chlorophyll-a concentrations (≤50 µg/L). A preliminary early warning threshold of 175 pg ATP/mL corresponded with 5 µg/L chlorophyll-a to initiate increased monitoring (e.g., of cyanotoxins). Following oxidation processes (i.e., chlorine, chloramine, ozone, permanganate), ATP was demonstrated as an indicator of cell lysis and a threshold value of <100 pg/mL was recommended for complete release of intracellular cyanotoxins. ATP was also used to assess efficacy of copper (Cu(II)) treatment on cyanobacteria-laden surface water. While 24-h exposure to 2.5 mg Cu(II)/L did not impact chlorophyll-a, ATP decreased from 13,500 to 128 pg/mL indicating metabolic activity was minimized. Ultimately, ATP analysis holds promise for early detection and mitigation of potentially harmful algal blooms based on superior sensitivity, independence from cell morphology artifacts, rapid time for analysis (<10 min), and ease of deployment in the field compared to conventional methods.

Using upstream oxidants to minimize surface biofouling and improve hydraulic performance in GAC biofilters.

The combination of biological growth and particle loading can adversely affect hydraulic performance in drinking water biofilters. In this study, upstream oxidant addition was used to distribute biologically-derived filter clogging in granular activated carbon (GAC) biofilters. Oxidant penetration was assessed during pilot-scale operation and backwashing of dual media (GAC/sand) and multimedia (GAC/anthracite/sand) biofilters. Influent chlorine (HOCl), monochloramine (NH2Cl), and hydrogen peroxide (H2O2) residuals were optimized to react with the GAC surface in the upper portion of the filter media bed (depth < 0.5 m) to attenuate biomass development. As the oxidant residual was quenched by surface-mediated reaction with the filter media, biomass growth was promoted deeper in the filter bed (depth > 0.5 m). The oxidant-induced effects on biomass and hydraulic performance were monitored through measurements of adenosine triphosphate (ATP) and head loss accumulation at different media depths. Addition of oxidants (e.g., 0.6 mg Cl2/L HOCl) could decrease terminal head loss by 20% in dual media filters and 40% in multimedia filters. These hydraulic benefits were achieved without significantly affecting removal of assimilable organic carbon (AOC), total organic carbon (TOC), turbidity, and particle counts. Oxidant type, residual concentration, media type, media age, and media depth influenced the passage of oxidant residuals and distribution of filter biomass. When oxidants were added during backwashing, oxidant residual was quenched through the bed depth from a combination of reactions with GAC media and biofilm degradation. This attenuation of residual oxidant may prevent the oxidant residual from penetrating the entire bed depth, potentially compromising backwashing objectives.

Biofiltration for removal of BOM and residual ammonia following control of bromate formation.

Nitrification was developed within a biological filter to simultaneously remove biodegradable organic matter (BOM) and residual ammonia added to control bromate formation during the ozonation of drinking water. Testing was performed at pilot-scale using three filters containing sand and anthracite filter media. BOM formed during ozonation (e.g., assimilable organic carbon (396-572 microg/L), formaldehyde (11-20 microg/L), and oxalate (83-145 microg/L)) was up to 70% removed through biofiltration. Dechlorinated backwash water was required to develop the nitrifying bacteria needed to convert the residual ammonia (0.1-0.5 mg/L NH(3)-N) to nitrite and then to nitrate. Chlorinated backwash water resulted in biofiltration without nitrification. Deep-bed filtration (empty-bed contact time (EBCT) = 8.3 min) did not enhance the development of nitrification when compared with shallow-bed filtration (EBCT = 3.2 min). Variable filtration rates between 4.8 and 14.6 m/h (2 and 6 gpm/sf) had minimal impact on BOM removal. However, conversion of ammonia to nitrite was reduced by 60% when increasing the filtration rate from 4.8 to 14.6 m/h. The results provide drinking water utilities practicing ozonation with a cost-effective alternative to remove the residual ammonia added for bromate control.

Investigation of biotransformation, sorption, and desorption of multiple chemical contaminants in pilot-scale drinking water biofilters.

The evolving demands of drinking water treatment necessitate processes capable of removing a diverse suite of contaminants. Biofiltration can employ biotransformation and sorption to remove various classes of chemicals from water. Here, pilot-scale virgin anthracite-sand and previously used biological activated carbon (BAC)-sand dual media filters were operated for ∼250 days to assess removals of 0.4 mg/L ammonia as nitrogen, 50-140 µg/L manganese, and ∼100 ng/L each of trace organic compounds (TOrCs) spiked into pre-ozonated Colorado River water. Anthracite achieved complete nitrification within 200 days and started removing ibuprofen at 85 days. Limited manganese (10%) removal occurred. In contrast, BAC completely nitrified ammonia within 113 days, removed all manganese at 43 days, and exhibited steady state removal of most TOrCs by 140 days. However, during the first 140 days, removal of caffeine, DEET, gemfibrozil, naproxen, and trimethoprim decreased, suggesting a shift from sorption to biotransformation. Acetaminophen and sulfamethoxazole were removed at consistent levels, with complete removal of acetaminophen achieved throughout the study; ibuprofen removal increased with time. When subjected to elevated (1 µg/L) concentrations of TOrCs, BAC removed larger masses of chemicals; with a subsequent decrease and ultimate cease in the TOrCs spike, caffeine, DEET, gemfibrozil, and trimethoprim notably desorbed. By the end of operation, anthracite and BAC exhibited equivalent quantities of biomass measured as adenosine triphosphate, but BAC harbored greater microbial diversity (examined with 16S rRNA sequencing). Improved insight was gained regarding concurrent biotransformation, sorption, and desorption of multiple organic and inorganic contaminants in pilot-scale drinking water biofilters.

Microbial community characterization of ozone-biofiltration systems in drinking water and potable reuse applications.

Microbial community structure in the ozone-biofiltration systems of two drinking water and two wastewater treatment facilities was characterized using 16S rRNA gene sequencing. Collectively, these datasets enabled comparisons by facility, water type (drinking water, wastewater), pre-oxidation (ozonation, chlorination), media type (anthracite, activated carbon), media depth, and backwash dynamics. Proteobacteria was the most abundant phylum in drinking water filters, whereas Bacteroidetes, Chloroflexi, Firmicutes, and Planctomycetes were differentially abundant in wastewater filters. A positive correlation was observed between media depth and relative abundance of Cyanobacteria in drinking water filters, but there was only a slight increase in one alpha diversity metric with depth in the wastewater filters. Media type had a significant effect on beta but not alpha diversity in drinking water and wastewater filters. Pre-ozonation caused a significant decrease in alpha diversity in the wastewater filters, but the effect on beta diversity was not statistically significant. An evaluation of backwash dynamics resulted in two notable observations: (1) endosymbionts such as Neochlamydia and Legionella increased in relative abundance following backwashing and (2) nitrogen-fixing Bradyrhizobium dominated the microbial community in wastewater filters operated with infrequent backwashing. Bradyrhizobium is known to generate extracellular polymeric substances (EPS), which may adversely impact biofilter performance and effluent water quality. These findings have important implications for public health and the operation and resiliency of biofiltration systems.

Formation of oxidation byproducts from ozonation of wastewater.

Disinfection byproduct (DBP) formation in tertiary wastewater was examined after ozonation (O(3)) and advanced oxidation with O(3) and hydrogen peroxide (O(3)/H(2)O(2)). O(3) and O(3)/H(2)O(2) were applied at multiple dosages to investigate DBP formation during coliform disinfection and trace contaminant oxidation. Results showed O(3) provided superior disinfection of fecal and total coliforms compared to O(3)/H(2)O(2). Color, UV absorbance, and SUVA were reduced by O(3) and O(3)/H(2)O(2), offering wastewater utilities a few potential surrogates to monitor disinfection or trace contaminant oxidation. At equivalent O(3) dosages, O(3)/H(2)O(2) produced greater concentrations of assimilable organic carbon (5-52%), aldehydes (31-47%), and carboxylic acids (12-43%) compared to O(3) alone, indicating that organic DBP formation is largely dependent upon hydroxyl radical exposure. Bromate formation occurred when O(3) dosages exceeded the O(3) demand of the wastewater. Bench-scale tests with free chlorine showed O(3) is capable of reducing total organic halide (TOX) formation potential by at least 20%. In summary, O(3) provided superior disinfection compared to O(3)/H(2)O(2) while minimizing DBP concentrations. These are important considerations for water reuse, aquifer storage and recovery, and advanced wastewater treatment applications.

Ozone regeneration of granular activated carbon for trihalomethane control.

Spatial and temporal variations of trihalomethanes (THMs) in distribution systems have challenged water treatment facilities to comply with disinfection byproduct rules. In this study, granular activated carbon (GAC) and modified GAC (i.e., Ag-GAC and TiO2-GAC) were used to treat chlorinated tap water containing CHCl3 (15-21µg/L), CHBrCl2 (13-16µg/L), CHBr2Cl (13-14µg/L), and CHBr3 (3µg/L). Following breakthrough of dissolved organic carbon (DOC), GAC were regenerated using conventional and novel methods. GAC regeneration efficiency was assessed by measuring adsorptive (DOC, UV absorbance at 254nm, and THMs) and physical (surface area and pore volume) properties. Thermal regeneration resulted in a brief period of additional DOC adsorption (bed volume, BV, ∼6000), while ozone regeneration was ineffective regardless of the GAC type. THM adsorption was restored by either method (e.g., BV for ≥80% breakthrough, CHBr3 ∼44,000>CHBr2Cl ∼35,000>CHBrCl2 ∼31,000>CHCl3 ∼7000). Cellular and attached adenosine triphosphate measurements illustrated the antimicrobial effects of Ag-GAC, which may have allowed for the extended THM adsorption compared to the other GAC types. The results illustrate that ozone regeneration may be a viable in-situ alternative for the adsorption of THMs during localized treatment in drinking water distribution systems.