Search Results (136)

Chlorinated benzoquinones such as 2,6-dichlorobenzoquinone (DCBQ) are toxic disinfection by-products that may persist in treated waters, requiring post-treatment strategies. In this study, the photo-Fenton process was evaluated for DCBQ degradation, with a focus on the influence of pH on kinetics, oxidation behavior, and water quality evolution. Experiments were conducted using 50.0 mg/L DCBQ, 1.0 mg/L Fe²⁺, and 2.0 mM H₂O₂ under UV irradiation (150 W) within a pH range of 3.0–12.0. Degradation followed apparent second-order kinetics, with maximum rates at acidic pH. At initial pH 3.0–5.0, rapid pollutant removal was accompanied by efficient aromaticity (UV₂₅₄) and color elimination, intense dissolved oxygen consumption, transient turbidity peaks due to intermediate formation, and increases in total dissolved solids, indicating extensive oxidation and a high degree of organic matter transformation, as inferred from indirect physicochemical indicators. At near-neutral pH, oxidation was slower, with delayed aromatic and chromophoric decay and moderate accumulation of intermediates. Mildly alkaline conditions exhibited limited radical activity, stable turbidity, and reduced mineralization. Under strongly alkaline conditions, oxidation was largely inhibited, with persistent aromaticity and negligible oxygen consumption. These findings highlight the importance of integrating advanced oxidation processes with adsorption-based systems for efficient and sustainable water treatment of emerging contaminants. Full article

This study investigates the development and performance of polyolefin-based packaging materials reinforced with industrial mineral residues, specifically slate powder (SP) and bivalve shell powder (BSP). High-density polyethylene (HDPE) and polypropylene (PP) matrices were compounded with these fillers and processed by extrusion blow moulding to produce final prototypes. Thermal analyses (TGA and DSC) showed that incorporating SP and BSP does not compromise the thermal stability of the polymer matrices and increases stiffness in the filled formulations. Accelerated ageing (QUV, 200 h) revealed distinct photo-oxidative behaviours. PP and PP + BSP (30%) exhibited increased fragility and moderate colour changes, whereas PP + SP (10%) retained flexibility, indicating a partial protective effect of SP. HDPE-based formulations showed higher intrinsic UV resistance, with HDPE + BSP (30%) displaying excellent colour stability. Tensile tests before and after QUV exposure confirmed that fillers increase stiffness with limited influence on tensile strength. Air permeability results indicated that neat PP and HDPE were below the detection limit. At the same time, filled formulations exhibited measurable permeability, suggesting that filler incorporation may influence gas transport through interfacial effects. Overall, the results show that SP and BSP act as reinforcing additives and can modify functional properties such as stiffness and ageing resistance. However, their influence on barrier performance depends on the formulation and permeation mechanism. Full article

Metformin (MET) is a widely prescribed pharmaceutical compound used for the management of glucose levels and body weight. However, it is only partially metabolized in the human body, and a significant fraction is excreted unchanged, leading to its frequent detection in aquatic environments. Consequently, the removal of MET from wastewater has become a matter of increasing concern due to its potential impact on aquatic ecosystems. Furthermore, as a nitrogen-containing compound, MET has been extensively employed as a model pollutant to evaluate the performance of physical and chemical treatment technologies for pharmaceutical contaminants. This review aims to critically assess and summarize the efficiency and key limitations of various processes applied for MET removal. The reviewed approaches include physical–chemical treatments such as adsorption; biological treatments (activated sludge, biofiltration and phytoremediation), which rely on microbial metabolic activities or plant uptake to degrade or sequester metformin; and advanced oxidation processes (AOPs), such as ozonation, photolysis, photocatalysis, Fenton, and photo-Fenton systems. The efficiency of MET removal and mineralization is strongly dependent on the treatment method employed. Among the evaluated processes, the photo-Fenton reaction emerges as one of the most promising technologies, achieving high removal efficiencies under both ultraviolet (UV) and visible (Vis) irradiation. Full article

Textile wastewater remains one of the most challenging industrial effluents to remediate due to its intense and persistent coloration, high organic load, elevated salinity, and fluctuating pH and the presence of recalcitrant dye structures and auxiliary chemicals. Conventional physicochemical and biological treatments frequently achieve incomplete removal, generate secondary wastes, or fail under high-salt and toxic dye matrices. Advanced oxidation processes (AOPs) provide molecular-level degradation via reactive oxygen species (ROS), yet their deployment is often constrained by narrow operating windows, catalyst instability, chemical/energy demand, and scale-up limitations. In this context, metal–organic frameworks (MOFs) have emerged as tunable porous catalytic platforms that integrate adsorption and oxidation within a single architecture through controllable metal nodes, functional linkers, and engineered pore environments. This critical review reimagines textile effluent treatment through the lens of MOF-based hybrid catalysts, synthesizing progress across Fenton/photo-Fenton catalysis, photocatalytic MOFs, persulfate activation, and MOF-derived/composite systems. Mechanistic pathways are discussed by linking pollutant enrichment, cyclic redox reactions, charge-transfer processes, and ROS-driven degradation toward mineralization, with emphasis on the distinction between rapid decolorization and true organic removal. A critical comparison highlights how hybridization improves charge transport, stability, and catalyst recovery, while persistent gaps remain in hydrolytic robustness, metal leaching control, intermediate toxicity assessment, real-wastewater validation, continuous-flow reactor integration, and techno-economic feasibility. Finally, the review outlines actionable research directions, including water-stable and defect-engineered MOFs, immobilized and structured catalysts, solar-driven operation, standardized performance metrics, and life-cycle-informed design, to accelerate translation toward scalable and sustainable textile wastewater remediation. By bridging material chemistry with reactor-level feasibility and sustainability assessment, this review provides an implementation-oriented perspective for next-generation textile wastewater treatment. Full article

Advanced oxidation processes based on photo-Fenton chemistry have gained increasing attention as effective treatment alternatives for the removal of pharmaceutical contaminants from water and wastewater systems. However, large-scale implementation remains constrained by operational requirements, limited mineralization efficiency, and challenges associated with process stability and selectivity. This review provides a critical assessment of recent advances (2022–2025) in conventional photo-Fenton and hybrid systems, including photocatalysis/photo-Fenton and sono-photo-Fenton processes, with emphasis on their performance in water and wastewater treatment applications. The removal of non-steroidal anti-inflammatory drugs, antibiotics, pharmaceutical mixtures, and real wastewater matrices is analyzed considering catalyst configuration, irradiation sources, oxidant utilization, and operating conditions relevant to practical treatment scenarios. Conventional homogeneous Fe²⁺/H₂O₂ systems enable rapid contaminant degradation but typically require acidic conditions and show limited mineralization efficiency. In contrast, iron-complexed and heterogeneous catalysts allow operation under near-neutral pH and visible-light irradiation, improving applicability in realistic water treatment systems. Hybrid photocatalysis/photo-Fenton processes enhance treatment efficiency through synergistic generation of reactive oxygen species, while ultrasound-assisted systems further intensify oxidation rates and contaminant removal. Special attention is given to oxidation mechanisms, catalyst stability, transformation products, and toxicity evolution to identify the key factors controlling treatment performance. Finally, current technological limitations, operational challenges, and design considerations for process integration, scale-up, and sustainable implementation in water and wastewater treatment are discussed. Full article

Increasing water demand and the rising complexity of wastewater matrices, driven by pharmaceuticals, personal care products, and recalcitrant industrial contaminants, require advanced catalytic solutions capable of efficient mineralization under sustainable conditions. Solar-driven processes have attracted growing attention; however, ultraviolet disinfection, heterogeneous photocatalysis, and photo-Fenton systems are commonly treated as independent approaches without mechanistic integration. This review presents a unified photonic–thermal catalytic framework for solar-driven wastewater treatment, emphasizing the interplay between photon absorption, charge-carrier separation, reactive oxygen species generation, and radical-mediated oxidation pathways. The contributions of ultraviolet, visible, and infrared radiation are analyzed in terms of catalyst activation, persulfate and ozone activation mechanisms, and temperature-enhanced reaction kinetics governed by Arrhenius behavior. Particular attention is given to photothermal effects that modulate surface reaction rates, mass transfer, and catalyst stability. By integrating mechanistic insights with reactor-level considerations, this work provides a rational basis for the design of robust solar catalytic systems with enhanced activity, selectivity, and scalability for real wastewater applications. Full article

Given the increasing environmental degradation, this study investigates advanced zinc oxide (ZnO)-based materials for the mineralization of toxic compounds through the combined action of photo- and piezocatalysis. Two complementary strategies were employed to enhance catalytic efficiency. First, ZnO_1−xN_x thin films were deposited by reactive high-power impulse magnetron sputtering (R-HiPIMS) to reduce the band gap energy. Second, flower-like ZnO nanostructures were synthesized using the pulsed thermionic vacuum arc (p-TVA) technique to increase the specific surface area. Both systems were further modified by decoration with Ag₂O nanoparticles to improve charge separation. The R-HiPIMS technique offers significant advantages in terms of precise control over processing parameters, enabling accurate tuning of film properties, including microstructure, chemical composition, and electronic structure. However, films produced via R-HiPIMS generally exhibit lower photo-piezocatalytic activity compared to nanostructured counterparts, primarily due to their comparatively reduced effective surface area and limited charge separation efficiency. In contrast, the p-TVA technique enables the synthesis of nanostructured thin films with substantially enhanced photo-piezocatalytic performance. This improvement is attributed to the increased effective surface area and the promotion of more efficient electron–hole pair separation. The materials were comprehensively characterized in terms of optical properties (UV–Vis spectroscopy), chemical composition and bonding (XPS), crystalline structure (XRD), surface morphology (FE-SEM), and photo-piezocatalytic performance. Catalytic activity was evaluated via the degradation of methylene blue (MB) under visible light irradiation and mechanical vibrations. Nitrogen incorporation in ZnO_1−xN_x thin films led to an increase in photocatalytic efficiency from 20% to 28.7%, while the simultaneous application of light and mechanical stimulation increased efficiency to approximately 50%. Under identical irradiation conditions, Ag₂O-decorated ZnO and Ag₂O-decorated ZnO_1−xN_x exhibited photo-degradation reaction rate constants up to 65% higher than bare counterparts, attributed to reduced electron–hole recombination. ZnO nanostructures achieved degradation efficiencies of 59%, rising to 88.3% with Ag₂O decoration under solar illumination for 120 min. When combined with mechanical vibrations, after 60 min, the degradation efficiencies reached 93% for ZnO and 98% for Ag₂O/ZnO systems. A photodegradation mechanism of Ag₂O NPs-decorated ZnO heterostructures was proposed. Full article

A ceramic anode made of Sb-doped SnO₂ and coated with a photoactive BiPO₄ layer was tested for the (photo)electrochemical oxidation of three commonly used pharmaceuticals: atenolol, ibuprofen, and norfloxacin. Light-pulsed chronoamperometry showed that the photoanode responded immediately to illumination. The application of light and current enhanced degradation for all compounds when treated separately. Ibuprofen and norfloxacin exhibited higher degradation than mineralization, which demonstrates their persistent nature. Electric current was essential to achieve efficient degradation and mineralization, demonstrating the effectiveness of the electrochemical approach. For multicomponent mixtures, applying light resulted in higher mineralization compared to dark conditions at low operation currents (0.2 A). At higher currents (0.4–0.8 A), the contribution of light was partially masked by the enhanced electrochemical production of hydroxyl radicals. The analysis of individual compounds within the mixture revealed significant improvements in degradation under light exposure. Overall, these results demonstrate the potential of the Sb-doped SnO₂ ceramic photoanode as a cost-effective and promising alternative to commercial materials for treating pharmaceutical contaminants. Full article

This study optimized a homogeneous photo-Fenton process for the simultaneous degradation of the emerging pesticides atrazine and methomyl in water using Response Surface Methodology (RSM). A synthetic agricultural effluent containing 2.0 mg L⁻¹ of each pesticide (COD = 103.2 mg O₂ L⁻¹; TOC = 26.1 mg C L⁻¹; BOD₅ = 45.8 mg O₂ L⁻¹) was treated in a recirculating UV–H₂O₂/Fe²⁺ reactor. A 2³ factorial design with replication and five central points identified the H₂O₂/Fe²⁺ ratio and irradiation time as the main factors controlling mineralization, achieving up to 88.9% COD removal in the best screening run. Steepest-ascent experiments were then performed to approach the region of maximum response, followed by a rotatable Central Composite Design (20 runs). The resulting quadratic model explained 98.14% of the COD variance (R² = 0.9814; adjusted R² = 0.9646; predicted R² = 0.8591; CV = 0.2736%) and predicted a maximum COD removal of 94.5% at a volumetric flow rate of 0.466 L min⁻¹, a Fenton ratio of 12.713 mg mg⁻¹, and a treatment time of 71.0 min. Experimental validation under these optimized conditions yielded highly reproducible removals of 94.2 ± 0.04% COD and 81% TOC, confirming the predictive capability of the RSM model and demonstrating a high degree of organic mineralization. The response surfaces revealed that increasing the Fenton ratio enhances oxidation up to an optimum, beyond which hydroxyl-radical self-scavenging slightly decreases efficiency. Overall, the integration of multivariable experimental design and RSM provided a robust framework to maximize photo-Fenton performance with moderate reagent consumption and operating time, consolidating this process as a viable alternative for the mitigation of pesticide-laden agricultural wastewaters. Full article

The presence of various drugs in wastewater has generated growing concern about the contamination of water bodies. This requires urgent attention and the development of effective methods for their degradation in aquatic ecosystems. The present study evaluates the efficiency of metformin (MET) degradation via various photochemical processes—photolysis, H₂O₂ photodecomposition, photocatalysis, and photo-Fenton—using iron-pillared bentonite clays (Fe-PILC) as a catalyst. The influence of radiation wavelength (254 nm and visible light) was investigated, while MET degradation, H₂O₂ consumption, and total organic carbon (TOC) removal were monitored as key response variables. Structural characterization confirmed successful pillaring, increasing the surface area of bentonite from 35 to 246 m²/g, with iron content at 11 wt. % quantified by atomic absorption spectroscopy. Fe₃O₄ and FeO were identified using XPS, and a 2.08 eV band-gap energy was revealed via diffuse reflectance spectroscopy. Experiments were conducted at environmentally relevant MET concentrations (13,000 ng L⁻¹) in a 0.1 L batch photoreactor at 25 °C. The results demonstrate that (i) photo-Fenton was the most efficient process to remove and mineralize MET (100% degradation after 10 min and 83% mineralization after 90 min); (ii) Fe-PILC is effectively activated at λ < 700 nm, enabling 75% mineralization under visible light; (iii) hydroxyl radicals and valence band holes were the primary oxidative species driving MET oxidation; and (iv) cyanoguanidine and carboxylic acids were identified as main oxidation by-products via UHPLC. Pseudo-first-order kinetic constants were determined for all processes, offering insight into their relative efficiencies. Notably, the rate constant for photo-Fenton under visible light (0.406 min⁻¹) was comparable to that under UV -light (0.545 min⁻¹), highlighting the potential of visible light-driven treatments. Therefore, this study demonstrated the metformin degradation capability of iron-pillared clays under both visible and UV light. Full article

Per- and polyfluoroalkyl substances (PFAS) are a diverse group of synthetic fluorinated compounds widely used in industrial and consumer products due to their exceptional thermal stability and hydrophobicity. However, these same properties contribute to their environmental persistence, bioaccumulation, and potential adverse health effects, including hepatotoxicity, immunotoxicity, endocrine disruption, and increased cancer risk. Traditional water treatment technologies, such as coagulation, sedimentation, biological degradation, and even advanced membrane processes, have demonstrated limited efficacy in removing PFAS, as they primarily separate or concentrate these compounds rather than degrade them. In response to these limitations, photoassisted processes have emerged as promising alternatives capable of degrading PFAS into less harmful products. These strategies include direct photolysis using UV or VUV irradiation, heterogeneous photocatalysis with materials such as TiO₂ and novel semiconductors, light-activated persulfate oxidation generating sulfate radicals, and photo-Fenton reactions producing highly reactive hydroxyl radicals. Such approaches leverage the generation of reactive species under irradiation to cleave the strong carbon–fluorine bonds characteristic of PFAS. This review provides a comprehensive overview of emerging photoassisted technologies for PFAS removal from water, detailing their fundamental principles, degradation pathways, recent advancements in material development, and integration with hybrid treatment processes. Moreover, it discusses current challenges related to energy efficiency, catalyst deactivation, incomplete mineralization, and scalability, outlining future perspectives for their practical application in sustainable water treatment systems to mitigate PFAS pollution effectively. Full article

The presence of acetaminophen (ACTP) in aquatic environments has become a significant concern due to its environmental persistence and the potential formation of toxic transformation products. This study systematically compares the performance of three electrochemical advanced oxidation processes (EAOPs), electro-oxidation (EO), electro-Fenton (EF), and solar photo-electro-Fenton (SPEF), for the degradation and mineralization of ACTP in aqueous media using boron-doped diamond (BDD) electrodes. Reactions were conducted under varying operational parameters, including current densities (15–60 mA cm⁻²), initial ACTP concentrations (10–30 mg L⁻¹), and Fe²⁺ dosages. In the SPEF system, natural sunlight was utilized as the source of UV-A irradiation (30–35 W m⁻²). Among the evaluated processes, SPEF exhibited the highest degradation efficiency, achieving up to 97% ACTP removal and 78% chemical oxygen demand (COD) reduction within 90 min. High-performance liquid chromatography (HPLC) analysis identified phenol and catechol as major intermediates, suggesting a degradation pathway involving hydroxylation, aromatic ring cleavage, and subsequent oxidation into low-molecular-weight carboxylic acids. Kinetic modeling revealed pseudo-first-order behavior, with a maximum rate constant of 0.0865 min⁻¹ under optimized conditions determined via Box–Behnken experimental design. Additionally, SPEF demonstrated enhanced energy efficiency (~0.052 kWh gCOD⁻¹) and improved oxidant regeneration under solar radiation, highlighting its potential as an environmentally friendly and cost-effective alternative for pharmaceutical wastewater treatment. These results support the implementation of SPEF as a sustainable strategy for mitigating the environmental impact of emerging contaminants, especially in regions with high solar availability and limited technological resources. Full article

The continuous occurrence of steroidal pharmaceutical dexamethasone (DXM) in aqueous environments indicates the need for an efficient removal technology. The frequent detection of DXM in surface water could be substantially reduced by the application of photo-induced advanced oxidation technology. In the present study, Fe²⁺ and UVA-light activated peroxo compounds were applied for the degradation and mineralization of a glucocorticoid, 25.5 µM DXM, in ultrapure water (UPW). The treatment efficacies were validated in real spring water (SW). A 120 min target pollutant degradation followed pseudo first-order reaction kinetics when an oxidant/Fe²⁺ dose 10/1 or/and UVA irradiation were applied. Acidic conditions (a pH of 3) were found to be more favorable for DXM oxidation (≥99%) regardless of the activated peroxo compound. Full conversion of DXM was not achieved, as the maximum TOC removal reached 70% in UPW by the UVA/H₂O₂/Fe²⁺ system (molar ratio of 10/1) at a pH of 3. The higher efficacy of peroxymonosulfate-based oxidation in SW could be induced by chlorine, bicarbonate, and carbonate ions; however, it is not applicable for peroxydisulfate and hydrogen peroxide. Overall, consistently higher efficacies for HO^•-dominated oxidation systems were observed. The findings from the current paper could complement the knowledge of oxidative removal of low-level DXM in real water matrices. Full article

Photocatalytic redox processes significantly contribute to shaping Earth’s surface environment. Semiconductor minerals exhibiting favorable photocatalytic properties are ubiquitous on rock and soil surfaces. However, the sunlight-responsive characteristics and functions of TiO₂, an excellent photocatalytic material, within natural systems remain incompletely understood, largely due to its wide bandgap limiting solar radiation absorption. This study analyzed surface coating samples, determining their elemental composition, distribution, and mineralogy. The analysis revealed enrichment of anatase TiO₂ and β-carotene. Informed by these observations, laboratory simulations were designed to investigate the synergistic effect of β-carotene on the sunlight-responsive behavior of anatase. Results demonstrate that β-carotene-sensitized anatase exhibited a 64.4% to 66.1% increase in photocurrent compared to pure anatase. β-carotene sensitization significantly enhanced anatase’s electrochemical activity, promoting rapid electron transfer. Furthermore, it improved interfacial properties and acted as a photosensitizer, boosting photo-response characteristics. The sensitized anatase displayed a distinct absorption peak within the 425–550 nm range, with visible light absorption increasing by approximately 17.75%. This study elucidates the synergistic mechanism enhancing the sunlight response between anatase and β-carotene in natural systems and its broader environmental implications, providing new insights for research on photocatalytic redox processes within Earth’s critical zone. Full article

In this study, the degradation of Nile Blue dye was investigated using homogeneous and heterogeneous photocatalytic methods based on the photo-Fenton reaction. More specifically, for homogeneous photocatalysis, the classical photo-Fenton (UV/Fe²⁺/H₂O₂) and modified photo-Fenton-like (UV/Fe²⁺/S₂O₈²⁻) systems were studied, while for heterogeneous photocatalysis, a commercial MOF catalyst, Basolite F300, and a natural ferrous mineral, geothite, were employed. Various parameters—including the concentrations of the oxidant and catalyst, UV radiation, and pH—were investigated to determine their influence on the reaction rate. In homogeneous systems, an increase in iron concentration led to an enhanced degradation rate of the target compound. Similarly, increasing the oxidant concentration accelerated the reaction rate up to an optimal level, beyond which radical scavenging effects were observed, reducing the overall efficiency. In contrast, heterogeneous systems exhibited negligible degradation in the absence of an oxidant; however, the addition of oxidants significantly improved the process efficiency. Among the tested processes, homogeneous techniques demonstrated a superior efficiency, with the conventional photo-Fenton process achieving complete mineralization within three hours. Kinetic analysis revealed pseudo-first-order behavior, with rate constants ranging from 0.012 to 0.688 min⁻¹ and correlation coefficients (R²) consistently above 0.90, confirming the reliability of the applied model under various experimental conditions. Nevertheless, heterogeneous techniques, despite their lower degradation rates, also achieved high removal efficiencies while offering the advantage of operating at a neutral pH without the need for acidification. Full article