Characterization of advanced wastewater treatment with ozone and activated carbon using LC-HRMS based non-target screening with automated trend assignment.

Advanced treatment is increasingly being applied to improve abatement of micropollutants in wastewater effluent and reduce their load to surface waters. In this study, non-target screening of high-resolution mass spectrometry (HRMS) data, collected at three Swiss wastewater treatment plants (WWTPs), was used to evaluate different advanced wastewater treatment setups, including (1) granular activated carbon (GAC) filtration alone, (2) pre-ozonation followed by GAC filtration, and (3) pre-ozonation followed by powdered activated carbon (PAC) dosed onto a sand filter. Samples were collected at each treatment step of the WWTP and analyzed with reverse-phase liquid chromatography coupled to HRMS. Each WWTP received a portion of industrial wastewater and a prioritization method was applied to select non-target features potentially resulting from industrial activities. Approximately 37,000 non-target features were found in the influents of the WWTPs. A number of non-target features (1207) were prioritized as likely of industrial origin and 54 were identified through database spectral matching. The fates of all detected non-target features were assessed through a novel automated trend assignment method. A trend was assigned to each non-target feature based on the normalized intensity profile for each sampling date. Results showed that 73±4% of influent non-target features and the majority of industrial features (89%) were well-removed (i.e., >80% intensity reduction) during biological treatment in all three WWTPs. Advanced treatment removed, on average, an additional 11% of influent non-target features, with no significant differences observed among the different advanced treatment settings. In contrast, when considering a subset of 66 known micropollutants, advanced treatment was necessary to adequately abate these compounds and higher abatement was observed in fresh GAC (7,000-8,000 bed volumes (BVs)) compared to older GAC (18,000-48,000 BVs) (80% vs 56% of micropollutants were well-removed, respectively). Approximately half of the features detected in the WWTP effluents were features newly formed during the various treatment steps. In ozonation, between 1108-3579 features were classified as potential non-target ozonation transformation products (OTPs). No difference could be observed for their removal in GAC filters at the BVs investigated (70% of OTPs were well-removed on average). Similar amounts (67%) was observed with PAC (7.7-13.6 mg/L) dosed onto a sand filter, demonstrating that a post-treatment with activated carbon is efficient for the removal of OTPs.