Microplastics (MPs) are detected in the water, sediments, as well as biota, mainly as a consequence of the degradation of plastic products/waste under environmental conditions. Due to their potentially harmful effects on ecosystems and organisms, MPs are regarded as emerging pollutants. The highly problematic aspect of MPs is their interaction with organic and inorganic pollutants; MPs can act as vectors for their further transport in the environment. The objective of this study was to investigate the effects of ageing on the changes in physicochemical properties and size distribution of polyethylene terephthalate (PET), as well as to investigate the adsorption capacity of pristine and aged PET MPs, using pharmaceutical diclofenac (DCF) as a model organic pollutant. An ecotoxicity assessment of such samples was performed. Characterization of the PET samples (bottles and films) was carried out to detect the thermooxidative aging effects. The influence of the temperature and MP dosage on the extent of adsorption of DCF was elucidated by employing an empirical modeling approach using the response surface methodology (RSM). Aquatic toxicity was investigated by examining the green microalgae Pseudokirchneriella subcapitata. It was found that the thermooxidative ageing process resulted in mild surface changes in PET MPs, which were reflected in changes in hydrophobicity, the amount of amorphous phase, and the particle size distribution. The fractions of the particle size distribution in the range 100–500 μm for aged PET are higher due to the increase in amorphous phase. The proposed mechanisms of interactions between DCF and PET MPs are hydrophobic and π–π interactions as well as hydrogen bonding. RSM revealed that the adsorption favors low temperatures and low dosages of MP. The combination of MPs and DCF exhibited higher toxicity than the individual components.

Polyethylene terephthalate (PET) microplastics constitute a significant portion of plastic pollution in the environment and pose substantial environmental challenges. In this study, the effectiveness of the Fenton process and post-oxidation coagulation for the removal of non-weathered and UV-weathered PET microplastics (PET MPs) were investigated. A response surface methodology was used to investigate the interplay between PET concentration and ferrous ion (Fe²⁺) concentration. The models revealed an intricate interplay between these variables, highlighting the need for a balanced system for optimal PET MP removal. For non-weathered PET, the simultaneous increase in the concentrations of both PET microplastics and Fe²⁺ was found to enhance the removal efficiency. However, this synergistic effect was not observed in UV-weathered PET, which also demonstrated a more pronounced effect from the Fe²⁺ concentration. The statistical analysis provided a strong basis for the validity of the models. X-ray photoemission spectroscopy (XPS) further elucidated the mechanisms behind these findings, revealing that UV weathering results in surface changes, which facilitate hydroxyl radical oxidation. These findings underline the complexity of the Fenton process in PET microplastic removal and the different behavior of non-weathered and UV-weathered microplastics. This has significant implications for tailoring remediation strategies and underscores the importance of considering environmental weathering in these strategies.

Olive oil phenols are recognized as molecules with numerous positive health effects, many of which rely on their antioxidative activity, i.e., the ability to transfer hydrogen to radicals. Proton-coupled electron transfer reactions and hydrogen tunneling are ubiquitous in biological systems. Reactions of olive oil phenols, hydroxytyrosol, tyrosol, oleuropein, oleacein, oleocanthal, homovanillyl alcohol, vanillin, and a few phenolic acids with a DPPH• (2,2-diphenyl-1-picrylhydrazyl) radical in a 1,4-dioxane:water = 95:5 or 99:1 v/v solvent mixture were studied through an experimental kinetic analysis and computational chemistry calculations. The highest rate constants corresponding to the highest antioxidative activity are obtained for the ortho-diphenols hydroxytyrosol, oleuropein, and oleacein. The experimentally determined kinetic isotope effects (KIEs) for hydroxytyrosol, homovanillyl alcohol, and caffeic acid reactions are 16.0, 15.4, and 16.7, respectively. Based on these KIEs, thermodynamic activation parameters, and an intrinsic bond orbital (IBO) analysis along the IRC path calculations, we propose a proton-coupled electron transfer mechanism. The average local ionization energy and electron donor Fukui function obtained for the phenolic compounds show that the most reactive electron-donating sites are associated with π electrons above and below the aromatic ring, in support of the IBO analysis and proposed PCET reaction mechanism. Large KIEs and isotopic values of Arrhenius pre-exponential factor A_H/A_D determined for the hydroxytyrosol, homovanillyl alcohol, and caffeic acid reactions of 0.6, 1.3, and 0.3, respectively, reveal the involvement of hydrogen tunneling in the process.

Sustainable hydrogen production is one of the main challenges today in the transition to a green and sustainable economy. Photocatalytic hydrogen production is one of the most promising technologies, amongst which BiVO₄-based processes are highly attractive due to their suitable band gap for solar-driven processes. However, the performance of BiVO₄ alone in this role is often unsatisfactory. Herein we report the improvement of BiVO₄ performance with reduced graphene oxide (rGO) as a co-catalyst for the photoelectrochemical water splitting (PEC-WS) in the presence of simple functionalized benzene derivatives (SFBDs), i.e., phenol (PH), benzoic acid (BA), salicylic acid (SA), and 5-aminosalicylic acid (5-ASA) as potential photogenerated hole scavengers from contaminated wastewaters. Linear sweep voltammetry and chronoamperometry, along with electrochemical impedance spectroscopy were utilized to elucidate PEC-WS performance under illumination. rGO has remarkably improved the performance of BiVO₄ in this role by decreasing photogenerated charge recombination. In addition, 5-ASA greatly improved current densities. After 120 min under LED illumination, 0.53 μmol of H₂ was produced. The type and concentration of SFBDs can have significant and at times opposite effects on the PEC-WS performance of both BiVO₄ and rGO-BiVO₄.