Search Results (211)

Persistent organic contaminants and complex wastewater matrices challenge conventional treatment because parent-compound removal does not necessarily imply mineralization, detoxification, or improved environmental safety. Advanced oxidation processes can address these limitations, but practical effectiveness is often constrained by oxidant activation, gas–liquid mass transfer, reagent distribution, light penetration, catalyst contact, energy demand, and matrix scavenging. This work critically examines hydrodynamic cavitation-assisted advanced oxidation processes for water and wastewater treatment, including systems based on hydrogen peroxide, ozone, Fenton and Fenton-like reactions, persulfate, peroxydisulfate, peroxymonosulfate, UV irradiation, photocatalysis, cold plasma, multi-hybrid configurations, and emerging reduction-oriented approaches. The discussion covers reactor configurations, target contaminants, real matrices, and sustainability-related performance metrics. The central argument is that hydrodynamic cavitation is not automatically sustainable as a stand-alone treatment. It becomes relevant as a sustainable intensification module only when measurable improvements are demonstrated in oxidant activation, mass transfer, treatment depth, biodegradability, toxicity reduction, process integration, or scale-up at acceptable energy and chemical cost. A reporting framework is proposed based on mineralization, COD/TOC reduction, by-products, toxicity, biodegradability, normalized energy consumption, chemical efficiency, real-matrix validation, reproducibility, and cost-relevant indicators. Future progress should move from isolated degradation tests to integrated, controllable, and scalable treatment frameworks. Full article

Manganese dioxide (MnO₂) modified biochar catalysts derived from biomass and waste polymer feedstocks were synthesized and evaluated as heterogeneous Fenton-like catalysts for solar-driven degradation of Rhodamine B (RhB) in aqueous systems. Biochars produced from maple wood and plastic waste (high-density polyethylene) provided porous carbon matrices with oxygen-rich surface functionalities that enabled effective MnO₂ loading and catalytic activity. Photocatalytic experiments conducted under real sunlight using a solar-collector reactor demonstrated faster RhB degradation compared to a conventional ultraviolet (UV) system, confirming the advantage of solar-driven operation. Complete RhB removal was achieved at initial concentrations of 100–300 ppm, whereas higher dye concentrations (500 ppm) exceeded the catalytic capacity within the tested reaction time. Kinetic analysis revealed catalyst-dependent reaction behaviors, indicating that degradation pathways were strongly influenced by the biopolymer-derived carbon structure and MnO₂ dispersion. Degradation efficiency was correlated with solar irradiance and reactor temperature, with higher UV index conditions enhancing catalytic performance. Reusability tests showed that the catalysts remained active over multiple cycles, although gradual decreases in reaction rates and catalyst recovery were observed. These results demonstrate the potential of biopolymer-derived carbon materials as effective solar-driven catalysts for wastewater treatment applications. Full article

In this work, three sulfur-iron materials (sulfide-modified nanoscale zerovalent iron (S-nZVI), ferrous sulfide (FeS), and pyrite (FeS₂)) were employed to enhance the Fenton process for naphthalene (NAP) degradation. The enhancement performance and mechanisms of S-nZVI, FeS, and FeS₂ were investigated and compared. The results showed that NAP removal was enhanced from 56.4% in the H₂O₂/Fe(II) system to 88.6%, 83.0%, and 89.1% with the addition of S-nZVI, FeS, and FeS₂, respectively. Three sulfur-iron materials could all reduce Fe(III) produced in aqueous solution, regenerate Fe(II), and slow down the precipitation of dissolved iron. In addition, the addition of sulfur-iron materials could promote the generation of hydroxyl radical (HO•), thus intensifying the degradation of NAP. The results of scavenging tests indicated that HO• was the dominant reactive oxygen species (ROS) for NAP removal, while superoxide radical (O₂⁻•) also participated. The effect of complex water matrices on NAP degradation was evaluated, showing that sulfur-iron material-enhanced techniques had a wide pH application range and had great tolerance to inorganic ions and humic acid. Moreover, NAP degradation intermediates and their toxicity were elucidated. Finally, the obvious removal of various pollutants in sulfur-iron material-enhanced systems demonstrated that these technologies could be used to remediate organic-polluted groundwater. Full article

The hematite phase decorated with iron-doped cerium oxide nanoparticles (F@FC) was precipitated from cerium and iron oxalate intermediate products. The photocatalytic composite of graphitic carbon nitride (gCN) and F@FC was prepared by a simple method involving mixing the two components, followed by thermal treatment at 400 °C. According to electron microscopy, F@FC is composed of a submicron iron oxide (hematite) phase decorated with iron-doped cerium oxide nanoparticles deposited on gCN substrate. A hierarchically structured composite was observed instead of a simple mechanical mixture of α-Fe₂O₃, Fe-CeO₂, and gCN. To observe two types of degradation activity, photocatalytic and Photo-Fenton degradation activity, Rhodamine B (RhB) was applied as the model water pollutant. The influence of the amount of photocatalyst, the RhB concentration, the presence of cations and anions, the pH, and the effect of e⁻, h⁺, •OH, and •O₂⁻ scavenging reactants were studied. The Photo-Fenton degradation exhibited high efficiency across the entire tested pH range, whereas photocatalytic degradation showed comparable activity only at acidic pH. The F@FC-gCN composite catalyst exhibited a high degree of recyclability. The degradation pathways of photocatalytic and Photo-Fenton reactions were suggested by HPLC-MS analysis of the reaction products. A notable finding of this study was the observation that the green-yellow, fluorescent intermediate Rhodamine 110 was formed during the photocatalytic degradation of RhB. However, the high reactivity of the generated •OH radicals during Photo-Fenton degradation has been demonstrated to inhibit the formation of intermediate Rhodamine 110. Full article

Polymeric electrolyte membranes based on a low equivalent-weight Aquivion^® commercial dispersion (D72-25BS; EW = 720 g eq⁻¹, Syensqo) were fabricated using a standardized in-house doctor-blade casting technique for application in proton exchange membrane fuel cells (PEMFCs). The low equivalent-weight (EW) Aquivion^® dispersion is a copolymer of tetrafluoroethylene (TFE) and sulfonyl fluoride vinyl ether (SFVE), commonly referred to as a short-side-chain (SSC) ionomer, which exhibits higher ion-exchange capacity (IEC) and proton conductivity than long-side-chain (LSC) perfluorosulfonic membranes. A home-made 30 wt.% Pt/CeO₂ radical scavenger (denoted syn-scavenger) was synthesized via a colloidal method and incorporated into the Aquivion^® membranes to investigate its mitigating effect on chemical degradation induced by peroxide radicals, a role typically associated with Ce-based scavengers. Particularly, the unique aspects of the Pt/CeO₂ scavenger synthesis could be summarized in the following points: (i) the mild aqueous deposition approach enabling highly dispersed Pt species on CeO₂ without the use of organic ligands; and (ii) the tailored redox interaction between Pt and ceria that enhances radical scavenging activity. Two Aquivion^® membranes (denoted Aqu) containing different syn-scavenger loadings (1.0 and 1.5 wt.%) were prepared and compared with a pristine Aquivion^® membrane and a membrane containing commercial CeO₂ (1.0 wt.%). Physicochemical characterization of the scavenger was performed using transmission electron microscopy (TEM), BET surface area analysis, and X-ray diffraction (XRD). The membranes were characterized by micro-Raman spectroscopy, water uptake and hydration number (λ), IEC, and proton conductivity measurements. To assess membrane stability, exsitu chemical oxidative degradation tests were conducted using Fenton’s reagent. Overall, the membrane containing 1.0 wt.% syn-scavenger emerged as the most promising candidate, exhibiting favourable chemical–physical properties and the lowest reductions in IEC and proton conductivity following the degradation test. Full article

In this study, the catalytic potential of peroxidase enzymes obtained from soybean industrial residues was investigated for the decolorization of the azo dye Direct Blue 2 (DB2) in textile wastewater. Peroxidase fractions (15 ± 5 U/L) were extracted and partially purified by ion-exchange chromatography and applied to a pilot-scale effluent, achieving DB2 degradation rates of 1.48 mg/L·h in the presence of chemical additives. High-performance liquid chromatography confirmed dye removal and detected benzidine (1 mg/L) as a degradation byproduct. Acute toxicity tests using Vibrio fischeri showed minimal variation, with values of 8 TU for untreated wastewater and 7.94 TU after enzymatic treatment. A subsequent Fenton process was implemented as a polishing step, achieving up to 90% decolorization, a 30% reduction in organic matter, and complete elimination of toxicity at an FeSO₄/H₂O₂ ratio of 1:2.4. The results demonstrate a sustainable strategy for pre-treating textile effluents containing azo dyes through the enzyme-based valorization of agro-industrial residues. Full article

Oxidative stress has been reported to be implicated in the pathogenesis of many neurodegenerative diseases, such as Alzheimer’s and Parkinson’s diseases. Enhancing antioxidant response, through the activation of the transcription factor Nrf2, may represent a potential strategy, based on in vitro models. To identify scaffolds potentially able to modulate the Nrf2-Keap1 interaction, docking experiments were carried out using a library of commercially available and in-house synthesized molecules. Compounds 1–4 were selected, and their direct and indirect antioxidant activity was evaluated in an acute oxidative stress model induced by Fenton’s reaction in the human neuroblastoma SH-SY5Y cell line. Results showed that these compounds exerted the most pronounced protective effect under the tested conditions at the following concentrations: 10 μM for 1, 25 μM for 2, 10 μM for 3, and 5 μM for 4. Moreover, these molecules notably decreased intracellular ROS production and lipid peroxidation by-products and increased the GSH/GSSG ratio. Furthermore, these molecules promoted the protein expression of antioxidant enzymes downstream of the Nrf2 transcriptional pathway. Interestingly, compound 3 resulted in being the most active among the four. Full article

Paracetamol (PAR) was selected as an emerging micropollutant model to evaluate the effectiveness of the photo-Fenton process using natural Bandjéli ore (BO) as a heterogeneous source of iron. An aliquot of 1 mL of the activated product was introduced into 200 mL of an aqueous solution of paracetamol at a defined concentration. The tests were conducted in a double-jacketed glass photoreactor (0.2 L), continuously stirred and equipped with two UVA PL-L lamps (36 W, λ = 365 nm), with the temperature maintained at 20 °C and the pH around 2.4. The photo-Fenton process was applied with different initial paracetamol concentrations (10–50 mg/L), different ${\mathrm{H}}_2{\mathrm{O}}_2/\mathrm{P}\mathrm{A}\mathrm{R}$ initial molar ratios (10:1 and 5:1), and different ferric ion concentrations (2.84–4.73 mg/L). Under these conditions, complete disappearance of the parent compound (paracetamol) was achieved in less than 3 h for iron contents below 5 mg/L, in compliance with the discharge standards applicable in France and Togo. Inhibition tests with propan-2-ol highlighted the predominant role of hydroxyl radicals and the secondary involvement of superoxide radicals in the subsequent stages. Taken together, these results demonstrate that Bandjéli iron ore is an effective, sustainable, and economically advantageous alternative to commercial iron salts for implementing the photo-Fenton process in the decontamination of water polluted by organic micropollutants. Full article

This work optimizes the energetic performance of 2,4,6-trinitrotoluene (TNT) abatement in water using a sono-photo-Fenton-like (SPF) process coupled with nano zero-valent iron (nZVI). A response–surface methodology (RSM) with a five-level central composite design (CCD) was applied to concurrently minimize specific energy consumption (SEC) from ultrasound (US) and UV irradiation while maximizing TNT removal. The optimal conditions were US power 80 W for 2 min and UV power 10 W for 6 min, yielding 73.95% TNT removal with SEC = 101.19 kWh kg⁻¹ TNT removed. The analysis of variance (ANOVA) test revealed that US power had the greatest effect on removal efficiency, whereas UV and US exposure times predominantly influenced SEC. Relative to the other Fenton-like configurations examined, the optimized SPF achieved superior removal at lower SEC and enabled enhanced iron recovery compared with photo-Fenton process using Fe²⁺. When applied to actual “yellow” wastewater, the optimized SPF again outperformed the photo-Fenton process using Fe²⁺, reducing SEC from 380.77 to 252.60 kWh kg⁻¹ and increasing treatment efficiency. The high-power/short-duration US paired with a low-power/short-duration UV regime provides a favorable efficacy–energy trade-off and supports pilot-scale deployment. Full article

To address the issues of hydrophobicity, easy fouling, and limited application of polyvinylidene fluoride (PVDF) membranes in water treatment processes, this study prepared Cu-MnO₂/GO/PVDF catalytic membranes via the immersion precipitation phase inversion method. Graphene oxide (GO) was incorporated to facilitate the construction of good water channels, while copper-doped manganese dioxide (Cu-MnO₂) was added to enhance catalytic activity. The structure, morphology, and performance of the membranes were characterized comprehensively. Results showed that Cu-MnO₂ was well interspersed between GO sheets, thereby increasing membrane surface roughness, effective filtration area, and hydrophilicity. The best catalytic membrane CM-5 exhibited the highest pure water flux (1391.20 L·m⁻²·h⁻¹) and methyl blue (MBE) rejection rate (98.06%), and it also displayed excellent reusability and stability. EPR tests confirmed the generation of HO· and HOO· in the Fenton-like system, which mediated dye degradation. The Cu-MnO₂/GO/PVDF catalytic membrane demonstrated excellent hydrophilicity, antifouling properties, and catalytic efficiency, thus providing a viable solution for dye wastewater treatment. Full article

Sexual dimorphism significantly influences the epidemiology of thyroid disorders, with females exhibiting higher incidence of thyroid diseases. Estrogens and their hydroxylated metabolites are key regulators of cellular redox balance and may contribute to sex-specific susceptibility through pro-oxidative mechanisms. However, the impact of individual estrogen metabolites on oxidative stress in thyroid follicular cells remains poorly defined. Here, we investigated the pro-oxidative effects of 17β-estradiol (E2) and its hydroxylated metabolites—2-hydroxyestradiol (2-OHE2), 4-hydroxyestradiol (4-OHE2), and 16α-hydroxyestrone (16α-OHE1)—in primary porcine thyroid cell cultures from males and females. Primary follicular thyroid cells were isolated from six male and six female pigs. Cells were exposed to E2 (100 nM) or its metabolites (1 μM), with or without Fenton reaction substrates (Fe²⁺ and H₂O₂), for 24 h. Lipid peroxidation (an index of oxidative damage to lipids) was quantified using BODIPY^® 581/591 C11 fluorescence via flow cytometry. Basal lipid peroxidation did not differ between sexes. 2-OHE2 increased lipid peroxidation in both male and female thyroid cells, with a more pronounced effect observed in males. In contrast, 4-OHE2 selectively enhanced lipid peroxidation only in female cells. 16α-OHE1 elevated lipid peroxidation in both sexes. E2 significantly increased lipid peroxidation in both male and female cells. Among all compounds tested, E2 exhibited the most potent pro-oxidative activity, particularly in female-derived cells. These findings provide novel insights into the redox-modulating effects of estrogen metabolism in the thyroid and suggest a potential molecular basis for sex-related susceptibility to thyroid dysfunction. While based on an in vitro porcine model, the study increases our understanding of the mechanisms by which estrogenic compounds may influence thyroid pathophysiology, possibly including early events in thyroid disease development or oncogenesis. Full article

Water pollution caused by synthetic dyes is a major environmental concern due to their stability, toxicity, and resistance to conventional wastewater treatments. This study presents a sustainable approach for synthesizing zinc oxide (ZnO) nanoparticles using artichoke biomass (waste) as a green precursor and enhancing their visible light photocatalytic activity through phosphorus doping. ZnO nanoparticles were successfully synthesized via a simple green route and doped with 3–6% phosphorus using NH₄H₂PO₄. The structural, morphological, and optical properties of the resulting P-ZnO were characterized by XRD, SEM/EDX, TEM, FTIR, and UV-Vis spectroscopy. (6 wt%) Phosphorus doping effectively reduced the band gap from 3.06 eV to 2.95 eV, extended light absorption into the visible range, and improved electron–hole separation, resulting in enhanced photocatalytic performance. The P-ZnO nanoparticles were evaluated for methylene blue (MB) degradation under visible light in a photo-Fenton-like process, with H₂O₂ as an oxidant. The degradation efficiency reached 87.05% with 6% P-ZnO and further increased to 92.35% upon addition of H₂O₂. Durability and reusability tests demonstrated that the 6% P-ZnO catalyst maintained its activity and structural integrity over four consecutive cycles, indicating negligible loss of efficiency and excellent resistance to surface poisoning. The photocatalytic activity was strongly impacted by the quantity of catalyst, solution pH, and initial dye levels, with optimal performance at 0.3 g/L catalyst loading, pH 3, and lower MB concentrations. Full article

The removal of synthetic dyes from industrial effluents remains challenging due to their chemical stability and poor biodegradability. Here we engineer metal-doped carbon dots (CDs) as heterogeneous Fenton-like catalysts and elucidate how dopant identity governs structure–activity relationships and reactive oxygen species (ROS) pathways. Fe-, Cu-, Zn- and Mg-doped CDs were prepared via a one-pot hydrothermal route and comprehensively characterised by TEM, FTIR, XPS and zeta-potential analysis. The resulting nanoparticles displayed narrow size distributions (10.2–15.2 nm) and dopant-dependent surface chemistries and charges. Catalytic tests with methylene blue (MB) and rhodamine B (RB) show that Fe-doped CDs deliver the highest activity toward MB degradation (k = 0.0218 min⁻¹), attributable to efficient Fe²⁺/Fe³⁺ redox cycling coupled with hydroxyl-rich surfaces that promote H₂O₂ activation. Zn-doped CDs achieve complete RB decolourisation under Fenton-like conditions, which we ascribe to their higher surface charge and abundant oxygenated sites that enhance pollutant adsorption and ROS generation. Cu- and Mg-doped CDs exhibit intermediate and dopant-specific performances consistent with their respective redox and adsorption characteristics. Collectively, these results establish clear correlations between dopant chemistry, surface functionality, and ROS formation routes, providing mechanistic guidance for the rational design of carbon-based Fenton catalysts for sustainable water remediation. Full article

Cu-modified ferrites, prepared by solvothermal syntheses, at up to 200 °C, show the presence of copper metal particles, embedded in ferrite nanocrystalline particle agglomerates. Notably, these metallic copper micron-sized crystallites were dramatically reduced in size, down to a few tens of nanometers, when part of the copper dopant was replaced by zinc. All materials were magnetic due to the presence of the cubic spinel phase, being ferrimagnetic, measured with external fields up to 6000 Oe, showing a narrow hysteresis of 89 Oe for the largest particle size copper ferrite material of 15 nm. Superparamagnetic behavior was observed for the smallest size, e.g., 11 nm, Cu-doped and the zinc-doped, 9–10 nm average particle size ferrites. The redox activity of the materials was studied in free-radical oxidation reactions (pH 7.4, physiological and pH 8.5, optimal) by the chemiluminescent method with (i) Fenton’s reagent (^·OH, ^·OOH); (ii) H₂O₂; and (iii) O₂^·− radicals. All materials presented extremely strong inhibitory activities (converted to prooxidant only at pH 7.4 in system iii, excluding the largest isolated copper-particle-containing material, which remained inhibitory). The materials’ antimicrobial potential was checked on Gram-positive and Gram-negative bacteria, Escherichia coli ATCC 25922, and Staphylococcus aureus ATCC 25923 via two classical methods, namely the spot and well diffusion tests in agar medium. The above tests included a nanocrystalline CuO, tenorite, as a reference material too. The Daphnia magna ecotoxicity test showed that all of the investigated materials are rather toxic, and since daphnia is a key component in freshwater ecosystems, the toxicity even at low concentrations may have significant consequences for the ecological balance. This requires careful monitoring and assessment of the possible use or disposal of these nanomaterials in the environment. Full article

We studied the impact of some magnetic nanoparticles on two wastewater models of Rhodamine B dye, with 5 µM and 10 µM concentrations. The magnetite nanoparticles, synthesized by the co-precipitation technique, having less than 20 nm diameter and typical crystallinity features, were used to treat the Rhodamine B solutions and the results were analyzed using spectral measurements. The biological efficacy of the photo-Fenton-like reactions underlying this wastewater treatment was assessed using the V79-4 fibroblast cell line of Chinese hamster. The MTT test (colorimetric method with 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide) was applied for the toxicity testing of Rhodamine B 10 µM and 5 µM, initially, and degraded with 8 g/L MNP and 10 mM hydrogen peroxide for 120 min of UV exposure, the cell viability decreasing to 57–59% and 69–74%, respectively, for the dose of 80 µL/mL. Morphological changes were identified by microscopy analysis, such as membrane disruption, cell content extravasation, apoptotic bodies, and also colored spherical inclusions suggesting non-metabolized dye solution aliquots. The simpler molecules consisting of Rhodamine B degradation products, i.e., benzoic acid, benzyloxyamine, and phthalic acid were analyzed for their theoretical reactivity through quantum chemical computational modeling, which revealed a significant chemical potential compared to Rhodamine B. Full article