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The threat of antibiotic resistance to the wellbeing of societies is well established. Urban wastewater treatment plants (UWTPs) are recognised sources for antibiotic resistance dissemination in the environment. Herein a novel cerium-doped zinc oxide (Ce-ZnO) photocatalyst is compared to ZnO and the benchmark TiO2-P25 in the immobilised form on a metallic support, to evaluate a photocatalytic process as a possible tertiary treatment in UWTPs. The catalysts were compared for the removal of two antibiotics, trimethoprim (TMP) and sulfamethoxazole (SMX), and for the inactivation of Escherichia coli (E. coli) strain DH5-Alpha in isotonic sodium chloride solution and of autochthonous bacteria in real secondary wastewater. In real wastewater, E. coli and other coliforms were monitored, as well as the respective fractions resistant to ofloxacin and azithromycin. In parallel, Pseudomonas aeruginosa and the respective sub-population resistant to ofloxacin or ciprofloxacin were also monitored. Photocatalysis with both ZnO and Ce-ZnO was faster than using TiO2-P25 at degrading the antibiotics, with Ce-ZnO the fastest against SMX but slower than undoped ZnO in the removal of TMP. Ce-ZnO catalyst reuse in the immobilised form produced somewhat slower kinetics maintained >50% of the initial activity, even after five cycles of use. Approximately 3 log10 inactivation of E. coli in isotonic sodium chloride water was recorded with reproducible results. In the removal of autochthonous bacteria in real wastewater, Ce-ZnO performed better (more than 2 log values higher) than TiO2-P25. In all cases, E. coli and other coliforms, including their resistant subpopulations, were inactivated at a higher rate than P. aeruginosa. With short reaction times no evidence for enrichment of resistance was observed, yet with extended reaction times low levels of bacterial loads were not further inactivated. Overall, Ce-ZnO is an easy and cheap photocatalyst to produce and immobilise and the one that showed higher activity than the industry standard TiO2-P25 against the tested antibiotics and bacteria, including antibiotic-resistant bacteria. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Exfoliated graphitic carbon nitride (g-C 3 N 4) was synthesised and characterized. • The metal-free photocatalyst was studied under visible light. • Efficient removal of micropollutants from secondary urban wastewater was achieved. • g-C 3 N 4 was supported on glass rings to avoid its recovery from treated wastewater. Abstract Heterogeneous photocatalysis under visible light was employed for the degradation of organic micropollutants (MPs) found in the biologically treated effluents of an urban wastewater treatment plant (UWWTP). The irradiation source consisted in 4 light emitting diodes (LEDs) with a nominal power of 400–500 W m–2 at 417 nm. Metal-free exfoliated graphitic carbon nitride (gCN T), which was synthetized through a simple thermal treatment using dicyandiamide as precursor, was employed as photocatalyst. The gCN T material was characterized using different techniques: N 2 adsorption isotherms at 77 K, electron microscopy (scanning and transmission) and diffuse reflectance UV–Vis. The photocatalytic performance of the material was compared to the commercial TiO 2 -P25, confirming that gCN T led to a remarkable higher removal efficiency of the target MPs. Most of these MPs were removed in less than 10 min to levels below the limit of quantification (carbamazepine > isoproturon > clopidogrel > diclofenac > atenolol > bezafibrate > tramadol > venlafaxine > fluoxetine). Indirect photolysis, resulting from the secondary reactive oxidants generated during the irradiation of the aqueous matrix components, was found to partially contribute for the elimination of the occurring MPs. In addition, the gCN T photocatalyst was immobilized on glass rings for use under continuous mode operation, a minimum residence time of 25 min being required to attain significant removal efficiencies. Phytotoxicity experiments showed that heterogeneous photocatalysis did not enhance the toxicity of the wastewaters. [ABSTRACT FROM AUTHOR]

[Display omitted] • TiO 2 was grown and crystallized on polysulfone, PTFE and PVDF membranes. • Diclofenac and 17α-ethinylestradiol were removed by adsorption and photocatalysis. • 17α-ethinylestradiol was preferentially adsorbed regardless of the membrane tested. • TiO 2 -polysulfone was the most active membrane for the removal of both pollutants. • TiO 2 -PVDF presented the highest stability in consecutive reaction cycles. TiO 2 in situ growth on three commercial membranes (polysulfone – PS, polyvinylidene fluoride – PVDF and polytetrafluoroethylene – PTFE) and its hydrothermal post-crystallization to transform TiO 2 into a photocatalytically-active phase, were investigated under mild synthesis conditions to preserve the textural properties of the supports. The membranes were successfully prepared and characterized by scanning electron microscopy, thermogravimetry analysis, N 2 physisorption, X-ray diffraction, and water contact angle measurements, among other techniques. Membrane supports with a more opened porosity and high hydrophilicity allowed to enhance the content and distribution of the anatase TiO 2 nanoparticles on the membrane surface. The efficiency and the permeate flux of the developed membranes were investigated to simultaneously remove diclofenac (DCF) and 17α-ethinylestradiol (EE2) from water by adsorption and UV–LED (light-emitting diode) photocatalysis under continuous recirculating mode. All TiO 2 membranes achieved removal efficiencies above 90% for both contaminants, EE2 being always preferentially adsorbed over DCF due to electrostatic repulsions between the DCF molecules and the surface of these membranes. The permeate flux of TiO 2 membranes was enhanced after UV-LED exposure as a consequence of the degradation of the contaminants adsorbed on the membrane surface during the dark phase. Moreover, the stability of TiO 2 nanoparticles on these membranes was studied by static tests under sonication and several consecutive reaction cycles. The TiO 2 membrane prepared with PVDF was the most stable, also presenting a high photocatalytic activity. [ABSTRACT FROM AUTHOR]