The presence of pharmaceutically active compounds (PhACs) in the wastewater effluents has confirmed that conventional wastewater treatment technologies are not sufficiently effective in the pharmaceuticals' removal. The objective of the present study was to evaluate and compare the photocatalytic degradation of PhACs using TiO 2 -P25, graphitic carbon nitride (g-C 3 N 4 , CN) and a heterojunction of perovskite strodium titanate and graphitic carbon nitride SrTiO 3 /g-C 3 N 4 (20% g-C 3 N 4 , 20CNSTO) photocatalytic materials, in hospital wastewater effluents, by simulated solar irradiation. The experiments were performed by using real wastewater samples collected from the university hospital wastewater treatment plant (WWTP) effluent of Ioannina city (Northwestern Greece) and inherent pharmaceutical concentration levels. The analysis of the samples was accomplished by solid phase extraction followed by liquid chromatography-Orbitrap high-resolution mass spectrometry. In the cases of TiO 2 and CN, more than 70% of the initial concentration (e.g., venlafaxine) was degraded after 90 min, while 20CNSTO presented lower photocatalytic performance. Furthermore, some compounds were sporadically detected (e.g., fluoxetine) or their concentrations remained stable during the photocatalytic treatment time period (e.g., trimethoprim). In total 11 transformation products (TPs) were formed along the degradation processes and were identified by using liquid chromatography high resolution mass spectrometry.
N-doped and N,S-co-doped SrTiO3 photocatalysts were prepared using glycine and L-histidine amino acids as nitrogen sources and L-cysteine as nitrogen and sulphur source. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 porosimetry, UV-Vis diffuse reflectance (DRS) and fluorescence spectroscopy, dynamic light scattering (DLS). Cubic SrTiO3 phase is formed in all samples, with crystal size ranged from 14.2 nm to 35.7 nm. The catalysts’ specific surface area and porosity depend on the amino acid dopant showing micro-mesoporosity for glycine, mesoporosity for histidine and non-porosity for cysteine. The lowest band gap (2.95 eV) was observed for the sample G-N-STO3 prepared with glycine (N:Sr:Ti 3:1:1 molar ratio) which produced also the higher amount of •OH radicals. The photocatalytic activity was tested against the degradation of methylene blue (MB) dye under UV-Vis and visible light irradiation following first-order kinetics.
Perovskite-structure SrTiO3 (STO) and graphitic carbon nitride (g-C3N4, CN) have attracted considerable attention in photocatalytic technology due to their unique properties, but also suffer from some drawbacks. The development of composite photocatalysts that combine properties of the individual semiconductors with enhanced charge separation is the current major trend in the photocatalysis field. In this study, SrTiO3/g-C3N4 (CNSTO) composites with different ratios (10, 20, 30, 40 and 50% g-C3N4) were prepared with a sonication mixing method. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 porosimetry, Fourrier transform infra-red spectroscopy (FT-IR), UV-Vis diffuse reflectance (DRS) and dynamic light scattering (DLS). STO spherical particles were successfully loaded on the g-C3N4 planes forming heterojunction composite materials. The photocatalytic activity was tested against the degradation of methylene blue (MB) dye under simulated solar light (SSL) irradiation following first-order kinetics. The photocatalytic activity followed the trend: 20CNSTO > 30CNSTO > 40CNSTO > 50CNSTO ≈ 10CNSTO, in accordance with the amount of •OH radicals determined by fluorescence spectroscopy. A Z-scheme mechanism was proposed for the enhanced photocatalytic degradation of MB as evidenced by trapping experiments with scavengers. Finally, significant stability and reusability was exhibited, indicating that such composites are of potential interest for photocatalytic treatments under sunlight irradiation.
Nowadays the occurrence and associated risks of Pharmaceutical Active Compounds (PhACs) in the aquatic environment comprises a major issue. In the present study, a comprehensive survey on contamination profiles, occurrence, removals, temporal variation and ecological risk of multiclass multiresidue PhACs, such as antibiotics, non-steroidal anti-inflammatories, lipid regulators and phsychiatrics, (including past and newly monitored PhACs as well as some of their metabolites) was performed in wastewaters from the WWTP of Ioannina University hospital along one year period on a monthly sampling basis. WWTP influent and effluent samples were analyzed for physicochemical quality parameters and PhACs concentration levels using Ultra High Performance Liquid Chromatography-Orbitrap-Mass Spectrometry (UHPLC-Orbitrap-MS), after Solid Phase Extraction (SPE) through Oasis HLB cartridges. Influent concentrations ranged between < LOQ (Limit of Quantification) for diclofenac and tolfenamic acid and 48586 ng/L for caffeine, while effluent concentrations between < LOQ for tolfenamic acid and simvastatin and 3361 ng/L for caffeine. Removal efficiencies ranged between −132.6% for venlafaxine and 100% for caffeine. Environmental risk assessment by means of Risk Quotient (RQ) for maximum and minimum concentration levels as well as optimized by the frequency of exceeding toxicity threshold values, RQ f , was applied revealing that up to 12 PhACs posed acute toxicity (clofibric acid, fenofibrate, sulfadiazine, sulfamethoxazole, trimethoprim, amitryptiline, fluoxetine, fluvoxamine, norfluoxetine, sertraline, venlafaxine, caffeine) while up to 4 compounds exerted long-term toxicity (sulfamethoxazole, fluoxetine, sertraline, caffeine) at least for one of the studied organisms. Furthermore, mixture RQ MEC/PNEC and RQ STU effect of multiple compounds showed high potential risks of the target groups in some cases, although some contaminants were not included due to lack of available data. Results can be used to prioritization of PhACs and their metabolites for surveillance in receiving water bodies as well as development of knowledge on toxicity and mechanism(s) of action.
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