In recent years, sewage treatment plants did not effectively remove emerging water pollutants, leaving potential threats to human health and the environment. Advanced oxidation processes (AOPs) have emerged as a promising technology for the treatment of contaminated wastewater, and the addition of catalysts such as heavy metals has been shown to enhance their effectiveness. This review focuses on the use of rare earth elements (REEs) as catalysts in the AOP process for the degradation of organic pollutants. Cerium and La are the most studied REEs, and their mechanism of action is based on the oxygen vacancies and REE ion concentration in the catalysts. Metal oxide surfaces improve the decomposition of hydrogen peroxide to form hydroxide species, which degrade the organics. The review discusses the targets of AOPs, including pharmaceuticals, dyes, and other molecules such as alkaloids, herbicides, and phenols. The current state-of-the-art advances of REEs-based AOPs, including Fenton-like oxidation and photocatalytic oxidation, are also discussed, with an emphasis on their catalytic performance and mechanism. Additionally, factors affecting water chemistry, such as pH, temperature, dissolved oxygen, inorganic species, and natural organic matter, are analyzed. REEs have great potential for enhancing the removal of dangerous organics from aqueous solutions, and further research is needed to explore the photoFenton-like activity of REEs and their ideal implementation for wastewater treatment.
Octocrylene is an organic sunscreen whose main action is to absorb UVB radiation and short UVA wavelengths; it is used in various cosmetic products in order to provide an adequate sun-protection factor or to protect the cosmetic formulations themselves from UV radiation. This filter is believed to be a possible endocrine disruptor and is also questioned due to its allergic and/or photoallergic potential. However, it continues to be widely used, and it has been found in various environments, not least those of swimming pools, where it is evidently released by consumers, to the point that it is now considered an emerging micropollutant. The present investigation presents the possible chemical fate of octocrylene in the typical chlorination conditions of wastewater or swimming pools. A total of 11 disinfection byproducts were identified, and 6 were identified for the first time, and separated by HPLC. These products were identified through careful mass spectrometry studies and 1D and 2D NMR experiments. A formation mechanism has been proposed that justifies the chemical structures of all of the compounds identified. The ecotoxicological assessment of octocrylene and their products was carried out by employing Phaeodactylum tricornutum, Brachionus plicatilis and Aliivibrio fischeri as bioindicators. The ecotoxicity results reveal that toxic byproducts might be generated during the oxidation process, increasing the potential risk to the marine environment.
Cyanobacterial blooms, a natural phenomenon in freshwater ecosystems, have increased in frequency and severity due to climate change and eutrophication. Some cyanobacteria are able to produce harmful substances called cyanotoxins. These metabolites possess different chemical structures and action mechanisms representing a serious concern for human health and the environment. The most studied cyanotoxins belong to the group of microcystins which are potent hepatotoxins. Anabaenopeptins are another class of cyclic peptides produced by certain species of cyanobacteria, including Planktothrix spp. Despite limited knowledge regarding individual effects of anabaenopeptins on freshwater organisms, reports have identified in vivo toxicity in representatives of freshwater zooplankton by cyanobacterial extracts or mixtures containing anabaenopeptins. This study focused on the isolation and toxicity evaluation of the cyanotoxins produced in the 2022 Planktothrix rubescens bloom in Averno lake, Italy. The three main cyclic peptides have been isolated and identified by nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS) and optical analyses as anabaenopeptins A and B, and oscillamide Y. Ecotoxicological tests on the aquatic model organisms Daphnia magna (crustacean), Raphidocelis subcapitata (algae), and Aliivibrio fischeri (bacterium) revealed that anabaenopeptins A and B do not generate significant toxicity at environmentally relevant concentrations, being also found a stimulatory effect on R. subcapitata in the case of anabaenopeptin A. By contrast, oscillamide Y displayed toxicity. Ecological implications based on ECOSAR predictions align with experimental data. Moreover, long-term exposure bioassays on different green unicellular algae species showed that R. subcapitata was not significantly affected, while Scenedesmus obliquus and Chlorella vulgaris exhibited altered growth patterns. These results, together with the already-known background in literature, highlight the complexity of interactions between organisms and the tested compounds, which may be influenced by species-specific sensitivities, physiological differences, and modes of action, possibly affected by parameters like lipophilicity.
The significantly increasing levels of Rare Earth Elements (REEs) in seawater are largely due to multiple anthropogenic activities. Their effects on marine primary producers such as Phaeodactylum tricornutum have not been fully assessed. This study focused on examining the long-term impacts of these two commonly occurring REEs, cerium (Ce) and gadolinium (Gd), on marine diatoms by 28 d of exposure. The 72 h effective concentrations that inhibited the growth of 20% (EC20) and 50% (EC50) of the exposed population were used for long-term exposures. The growth, oxidative stress level, photosynthetic pigments, and chlorophyll fluorescence were assessed in the diatoms, after 7, 14, 21, and 28 d of REEs exposure. Results display a difference in the toxicity induced by the two elements. Exposure to 2.39 mg/L (EC20) and 3.13 mg/L (EC50) of Ce, and to 4.52 mg/L (EC20) and 6.02 mg/L (EC50) of Gd displayed a lower effect on the growth of algae cells, as the response remained below 20% for inhibition or stimulation. Except for GD, the ROS and the activities of SOD, and LPO showed, during the exposure, comparable levels respect to control cells. A change in chlorophyll levels was also observed especially under Ce exposure. Both elements showed changes in photosynthetic performance. This study provides new insights into the different effects of Ce and Gd on P. tricornutum, demonstrating their diverse modes of action on this important primary producer. The findings provide further evidence of the adverse effects of anthropogenic REEs pollution on marine ecosystems.
The persistent occurrence of antibiotics like chloramphenicol (CAP) in aquatic systems poses serious environmental and public health risks. This study investigates the photocatalytic degradation of CAP using cerium oxide (CeO2), lanthanum oxide (La2O3), and lanthanum-doped cerium oxide (CexLayO2−δ), synthesized via co-precipitation. The catalysts were tested under a solar simulator, UV-A, and UV-C radiation, both with and without hydrogen peroxide (H2O2). Structural characterization confirmed successful synthesis of nanometric catalysts, with La doping causing lattice expansion in CeO2 and a reduction in crystallite size (from 27 nm in CeO2 to ~20 nm in doped samples). Photolysis alone achieved limited CAP removal (~34–35%), while photocatalysis with La2O3 under UV-A and UV-C improved removal up to 58% and 55%, respectively. Complete degradation was obtained with La2O3 under UV-C in the presence of H2O2 within 15 min. Pareto analysis highlighted the dominant effect of the interaction between radiation and H2O2 (43%), while the catalyst type contributed minimally (0.23%). These findings confirm the potential of REE oxides, especially La2O3, in advanced oxidation processes and underscore the importance of light source and radical generation over catalyst selection alone.
In this study, La2O3 and CeO2 nanopowders were prepared using a simple and cost-effective precipitation method. Wide-angle X-ray diffraction (WAXD), UV-Visible reflectance diffuses (UV-Vis DRS), Raman spectroscopy, and specific surface area were used to characterize the photocatalysts, evidencing that the used preparation method was effective in the generation of crystalline CeO2 and La2O3. In particular, WAXD results showed that the average crystallite size of the achieved La2O3 and CeO2 samples were about 22 nm and 28 nm, respectively. The photocatalytic performances of the prepared catalysts were investigated in the degradation of levofloxacin (LEV) and the inactivation of a waterborne pathogen levofloxacin resistant (Enterococcus faecalis ATCC 29212) by using a photoreactor equipped with a solar simulator (SS). After 120 min, the CeO2 and La2O3 photocatalytic treatments allowed us to achieve between 75% and 83% of levofloxacin removal, respectively. A complete removal of 106 CFU/mL Enterococcus faecalis ATCC 29212 was achieved after 5 and 60 min of La2O3 and CeO2 photocatalytic processes, respectively.