N-Nitrosodimethylamine Formation during UV/Hydrogen Peroxide and UV/Chlorine Advanced Oxidation Process Treatment Following Reverse Osmosis for Potable Reuse.

Chloramines applied to control microfiltration and reverse osmosis (RO) membrane biofouling in potable reuse trains form the potent carcinogen, N-nitrosodimethylamine (NDMA). In addition to degrading other contaminants, UV-based advanced oxidation processes (AOPs) strive to degrade NDMA by direct photolysis. The UV/chlorine AOP is gaining attention because of its potential to degrade other contaminants at lower UV fluence than the UV/hydrogen peroxide AOP, although previous pilot studies have observed that the UV/chlorine AOP was less effective for NDMA control. Using dimethylamine (DMA) as a model precursor and secondary municipal wastewater effluent, this study evaluated NDMA formation during the AOP treatment via two pathways. First, NDMA formation by UV treatment of monochloramine (NH2Cl) and chlorinated DMA (Cl-DMA) passing through RO membranes was maximized at 350 mJ/cm2 UV fluence, declining at higher fluence, where NDMA photolysis outweighed NDMA formation. Second, this study demonstrated that chlorine addition to the chloramine-containing RO permeate during the UV/chlorine AOP treatment initiated rapid NDMA formation by dark breakpoint reactions associated with reactive intermediates from the hydrolysis of dichloramine. At pH 5.7, this formation was maximized at a chlorine/ammonia molar ratio of 3 (out of 0-10), conditions typical for UV/chlorine AOPs. At 700 mJ/cm2 UV fluence, which is applicable to current practice, NDMA photolysis degraded a portion of the NDMA formed by breakpoint reactions. Lowering UV fluence to ∼350 mJ/cm2 when switching to the UV/chlorine AOP exacerbates effluent NDMA concentrations because of concurrent NDMA formation via the UV/NH2Cl/Cl-DMA and breakpoint chlorination pathways. Fluence >700 mJ/cm2 or chlorine doses greater than the 3:1 chlorine/ammonia molar ratios under consideration for the UV/HOCl AOP treatment are needed to achieve NDMA control.

Pharmaceuticals, pesticides, and ultraviolet filters in wastewater discharges to San Francisco Bay as drivers of ecotoxicity.

Research in the United States evaluating ecotoxic risk to receiving waters posed by contaminants occurring in wastewater discharges typically has focused on measurements of pharmaceuticals and personal care products (PPCPs), with limited evaluations of UV filters and phenylpyrazole and neonicotinoid pesticides. In this study, concentrations of 5 representative pharmaceuticals, 11 pesticides or pesticide degradation products, and 5 ultraviolet filters were measured in 24 h composite samples of six wastewater discharges representing ∼70% of the total wastewater discharged to San Francisco Bay during the summer and fall of 2021. No significant difference was observed between concentrations measured on weekdays vs. weekends. A hydrodynamic model of San Francisco Bay was used to estimate annual average dilution factors associated with different subembayments. With and without considering dilution effects, Risk Quotients were calculated using the 90th percentile of measured concentrations in wastewater effluents and threshold concentrations associated with ecotoxicity. Risk Quotients were highest for the neonicotinoid pesticide, imidacloprid, and exceeded ecotoxicity thresholds in the lower South Bay by a factor of 2.4, even when considering dilution. Compared to commonly measured pharmaceuticals, Risk Quotients for imidacloprid were higher than those for carbamazepine, trimethoprim and diclofenac, and comparable to those for propranolol and metoprolol. Risk Quotients for the pesticide, fipronil, and the UV filter, oxybenzone, were higher than for carbamazepine. The results highlight the need to incorporate pesticides and UV filters with high Risk Quotients into studies in the United States evaluating ecotoxic risk associated with contaminants in municipal wastewater discharges.

Control of sulfides and coliphage MS2 using hydrogen peroxide and UV disinfection for non-potable reuse of pilot-scale anaerobic membrane bioreactor effluent.

Anaerobic membrane bioreactors reduce the energy cost of wastewater treatment and meet filtration requirements for non-potable reuse. However, sulfides (H2S/HS-) formed during anaerobic treatment exert a high chlorine demand and inhibit UV disinfection by photon shielding at 254 nm. This study evaluated the feasibility of hydrogen peroxide (H2O2) for sulfide oxidation, UV disinfection for inactivation of MS2 bacteriophage, and chlorine to provide a residual for distribution. H2O2 treatment at pH ≥ 8 favored sulfide oxidation to sulfate in 30 min at a 4:1 H2O2:sulfide stoichiometry. Compared to a 6:1 H2O2:sulfide molar ratio, treatment of anaerobic effluent with 0.5 mM sulfides with a 4:1 H2O2:sulfide molar ratio would increase the applied UV fluence needed for 5-log MS2 inactivation from 180 mJ cm-2 to 225 mJ cm-2. However, the lower H2O2 dose reduced the dose of chlorine needed to quench residual H2O2 and provide a residual for distribution. Treatment at the 4:1 H2O2:sulfide molar ratio was favored, because the cost savings in H2O2 and chlorine reagents outweighed the energy savings associated with UV treatment. However, H2O2/UV/chlorine treatment of anaerobic effluent was cost-competitive with conventional treatment of aerobic effluent for non-potable reuse only for < 285 µM sulfides.