Solar photocatalysis application in UWWTP outlets - simulations based on predictive models in flat-plate reactors and pollutant degradation studies with in silico toxicity assessment

The application of the solar photocatalysis for the degradation of residual pollutants found in surface water was demonstrated. Semi-pilot scale flat-plate cascade reactor (FPCR) was used to study the degradation of model organic pollutants: enrofloxacin (ENRO), 17β-estradiol (E2) and 1H-benzotriazole (1H-BT) over TiO₂ thin-film supported on glass fibers. A modular panel with full-spectra solar lamps with appropriate UVB and UVA irradiation levels was used as a simulation of sunlight. Pollutant degradation in FPCR was estimated using predictive models; intrinsic reaction rate constants (k_i) for ENRO, E2 and 1H-BT independent of the reactor size, flow rate and irradiation conditions were determined: 9.60, 3.35 and 0.37 10⁹ s^-1 W^-0.5 m^1.5, respectively. Main degradation products (DPs), formed upon hydroxylation, ring opening and oxidation, were identified using LC-QTOF-MS. The ecotoxicological impact was assessed via T.E.S.T. and ECOSAR open-source tools showing the formation of less harmful DPs after sufficient reaction time. Pollutant degradation was simulated at four locations of interest, i.e. exhausts from urban wastewater treatment plants (UWWTPs) in Zagreb, Croatia (45°N), Krakow, Poland (50°N), Sevilla, Spain (37°N) and Ioannina, Greece (39.6°N). Results have proved that a simple flat-plate system with supported photocatalysts can be easily scaled up and incorporated at the outlet of UWWTP for the reduction of pollutant load and related toxicity. The exhaust canal in Zagreb with the estimated length of a photocatalytic layer of 122 m for the > 90% degradation of all target pollutants was discussed as the best installation site among studied locations. ENVIRONMENTAL IMPLICATION: A multi-disciplinary approach to the tentative application of TiO₂ solar photocatalysis outdoors to reduce pollutant loads and toxicity in surface waters was demonstrated. Possible application at four selected locations in Europe, as an additional step in water treatment after urban wastewater treatment plants (UWWTPs) was discussed. Target pollutants were studied under environmentally relevant conditions (sunlight levels, water matrix, simulation of process on a real scale at selected geographical location), at both higher and low concentrations.