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Sulfate radicals (SO) reactivity against gram-negative (E. coli) and gram-positive (E. faecalis) bacteria and Contaminants of Emerging Concern (CECs) (Diclofenac-DCF, Sulfamethoxazole-SMX and Trimethoprim-TMP) was investigated through laser flash photolysis (LFP) technique. Analysis of the lifetime of SO in presence of cell-wall compounds of bacteria and CECs allowed determining reactivity of SO towards these compounds. Results showed that SO reacts with common cell-wall components through H-abstraction mechanism (k < 10 Ms). By contrast, k > 10 Ms were found using aromatic amino acids (AAA) only present in Porins of the gram-negative outer-membrane. The intermediates detected from the reaction of SO with the AAA confirmed the involvement of electron transfer processes. Moreover, k values determined for DCF, TMP and SMX also agreed with an electron transfer mechanism. Interestingly, bacteria and CECs removal at pilot plant scale by UV-C/SO is in accordance with the k obtained using the LFP: E. coli > E. faecalis and DCF > TMP ≅ SMX., This work is part of a project that has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie Grant Agreement No 765860 (AQUAlity). Authors also acknowledge the Spanish Ministry of Science and Innovation (Projects PID2019–110441RB-C32 and PID2019–110441RB-C33). PhD Scholarship from CONACYT for J. Flores-Garcia (709358) is acknowledged.

The photocatalytic performance of pristine and rare earth elements (La, Ce, Pr, Er, Yb) doped zinc oxide was tested toward the abatement of a model pollutant in MilliQ water and wastewater matrices. ZnO doped with Ce, Er and particularly with Yb exhibited photoactivity higher than bare zinc oxide and the benchmark TiO2 P25, especially in wastewater matrix. Several electrochemical investigations were performed via chronopotentiometry and cyclic voltammetry aimed to shed light on the reasons why the diverse materials behaved differently. From the overall data a complex picture emerged, where there is not a single property of the materials evidently outperforming the others. Nonetheless, from the analysis of whole data a limited role of doping emerged for La and Pr, doping with Er improved the photocurrent, doping with Yb favored a better accumulation of photoelectrons, and doping with Ce promoted a faster electron transfer.

This work reports the effect of doping zinc oxide with lanthanide ions on structural, EPR and UV visible properties. Bare and doped samples were synthesized using the simple and green hydrothermal process. Different rare earth ions (RE = La, Ce, Pr, Er and Yb) with 1% molar ratio RE/Zn were used. The samples have been studied using X Ray Diffraction, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and UV visible diffuse reflectance spectroscopy. Finally, electron paramagnetic resonance (EPR) spectroscopy, was used to assess the materials photoactivity under UV irradiation, both in solid state, to see the charge carriers’ generation and in solution, evaluating the OH• radical formation using the DMPO (5,5-Dimethyl-1-Pyrroline-N-Oxide) spin trapping technique. The results suggest that the synthesized materials could be interesting systems for the photocatalytic abatement of emerging organic persistent pollutants in wastewater treatment plants.

This study investigates the effectiveness of non-activated peroxymonosulfate (PMS) as oxidative agent for water purification in the presence and absence of natural solar radiation. The inactivation of three pathogens (Escherichia coli, Enterococcus faecalis and Pseudomonas aeruginosa) and degradation of three Contaminants of Emerging Concern (CECs) (Trimethoprim-TMP, Sulfamethoxazole-SMX and Diclofenac-DCF) was simultaneously assessed in isotonic water (IW) by testing a wide range of PMS concentrations (from 0.0001 to 0.01 mM). A significant oxidative effect of PMS in darkness was obtained for both bacteria and CEC abatement, but when irradiated with solar light, results demonstrated a great enhancement on all bacterial kinetic rates, reaching >5 Log reduction in 30 min (1.5 kJL−1 of QUV) with 0.005 mM of oxidant as the best concentration. For CECs, higher degradation performance was obtained with 0.01 mM, 80% removal of DCF, SMX and TMP was achieved in 16 min (1.5 kJL−1), 27 min (9.4 kJL−1) and 150 min (16.8 kJL−1), respectively. Besides, the influence of inorganic species on the global PMS/solar system performance was assessed by testing its effectiveness in distilled water (DW), natural well water (WeW) and diluted well water (d-WeW) at 0.01 mM. Results revealed that (i) high chloride concentration (IW) has an important positive effect, (ii) the presence of a complex inorganic chemical water composition reduced the system efficiency (WeW), and (iii) no differences were obtained from the presence of low or high contents of carbonates/bicarbonates (WeW versus d-WeW), obtaining the following global PMS/solar efficiency performance order: IW > DW > WeW = d-WeW.

This study explores the capability of Sulfate Radical-based Advanced Oxidation Processes (SR-AOPs) for the simultaneous disinfection and decontamination of urban wastewater. Sulfate and hydroxyl radicals in solution were generated activating peroxymonosulfate (PMS) under UV-C irradiation at pilot plant scale. The efficiency of the process was assessed toward the removal of three CECs (Trimethoprim (TMP), Sulfamethoxazole (SMX), and Diclofenac (DCF)) and three bacteria (Escherichia coli, Enterococcus spp., and Pseudomonas spp.) in actual urban wastewater (UWW), obtaining the optimal value of PMS at 0.5 mmol/L. Under such experimental conditions, bacterial concentration ≤ 10 CFU/100 mL was reached after 15 min of UV-C treatment (0.03 kJ/L of accumulative UV-C radiation) for natural occurring bacteria, no bacterial regrowth was observed after 24 and 48 h, and 80% removal of total CECs was achieved after 12 min (0.03 kJ/L), with a release of sulfate ions far from the limit established in wastewater discharge. Moreover, the inactivation of Ampicillin (AMP), Ciprofloxacin (CPX), and Trimethoprim (TMP) antibiotic-resistant bacteria (ARB) and reduction of target genes (ARGs) were successfully achieved. Finally, a harmful effect toward the receiving aquatic environment was not observed according to Aliivibrio fischeri toxicity tests, while a slightly toxic effect toward plant growth (phytotoxicity tests) was detected. As a conclusion, a cost analysis demonstrated that the process could be feasible and a promising alternative to successfully address wastewater reuse challenges.