Search Results (83)

The ability of ultrasound/peracetic acid (US/PAA) to degrade the azo dye Sunset Yellow FCF (SSY) was evaluated considering the impacts of power, pH, inorganic carbon, common salts, radical scavengers, and real water matrices. Pseudo-first-order rate constants revealed synergy indices of 2.90, 3.28, 2.22, and 2.03 at electrical powers of 40, 60, 80, and 100 W, respectively. Selective scavenger assays revealed a mixed radical regime. ^•OH radical involvement was confirmed by inhibition with alcohols (tert-butanol, 2-propanol), benzoic acid, nitrobenzene, sodium azide, and phenol, while suppression by TEMPO highlighted the key role of PAA-derived acyl and peroxyl radicals. Nitrobenzene caused pronounced inhibition at elevated doses, while nitrite acted as a decisive quencher by converting ^•OH and other oxidants into less reactive species. Carbonate alkalinity exerted dual effects: at acidic pH (3.7–4.4) it diverted ^•OH radicals to carbonate radicals and reduced cavitation through dissolved CO₂, whereas at near-neutral pH it buffered conditions toward the optimum (pH 9) and enhanced degradation. Common anions (chloride, sulfate, nitrate) at ≤10 mM produced minor effects. Tests in environmental waters revealed the following reactivity order: seawater > ultrapure water > tap water ≈ Zamzam water > tertiary effluent. Enhanced performance in seawater was attributed to halide-mediated formation of reactive chlorine and bromine species, while inhibition in effluent was linked to organic matter scavenging. Overall, US/PAA emerges as a robust and adaptable advanced oxidation process for azo dye abatement across diverse water matrices. Full article

The photoinitiation properties of two porphyrins were evaluated for the free-radical photopolymerization (FRP) of a bio-based acrylated monomer, i.e., soybean oil acrylate (SOA). Their combination with various co-initiators, such as a tertiary amine as electron donor (MDEA), an iodonium salt as electron acceptor (Iod), as well as two biosourced co-initiators used as H-donors (cysteamine and N-acetylcysteine), makes them highly efficient photoinitiating systems for FRP under visible light irradiation. Electron paramagnetic resonance spin trapping (EPR ST) demonstrated the formation of highly reactive radical species, and fluorescence and laser flash photolysis highlighted the chemical pathways followed by the porphyrin-based systems under light irradiation. High acrylate conversions up to 96% were obtained with these different systems at different irradiation wavelengths (LEDs@385 nm, 405 nm, 455 nm, and 530 nm), in laminate or under air. The final crosslinked and bio-based porphyrin-based materials were used for the full photo-oxidation in water of an azo-dye (acid red 14) and under UV irradiation. These materials have been involved in three successive depollution cycles without any reduction in their efficiency. Full article

Bimetallic mesoporous photocatalysts were synthesized via a wet impregnation method using SBA-15 as a support, and characterized by UV–visible diffuse reflectance spectroscopy, low-angle X-ray diffraction and N₂ physisorption. Among the tested materials, the Ti/Mn combination exhibited the highest photocatalytic activity in azo dye degradation. To understand this enhanced performance, catalysts with varying Mn loads and calcination ramps were evaluated. Additionally, experiments with radical scavengers (isopropanol, chloroform) and under N₂ insufflation were conducted to identify the active radical species. Catalysts prepared with low Mn content and higher calcination ramps showed the greatest activity, which significantly decreased with isopropanol, indicating hydroxyl radicals as the main reactive species. In contrast, samples with higher Mn content and quicker heating displayed reduced activity in the presence of chloroform, suggesting superoxide radical involvement. Spectroscopic analyses (XPS, UV–Vis DRS) revealed that increasing Mn load promotes the formation of Mn²⁺ over Mn⁴⁺ species and lowers the band gap energy. These findings highlight the direct correlation between synthesis parameters, surface composition and optical properties, providing a strategy for fine-tuning the performance of a photocatalyst. Full article

Persistent reactive azo dyes released from textile finishing are a serious threat to water systems, but effective methods using sunlight to break them down are still limited. Everzol Yellow 3RS (EY-3RS) is particularly recalcitrant: past studies have relied almost exclusively on physical adsorption onto natural or modified clays and zeolites, and no photocatalytic pathway employing engineered nanomaterials has been documented to date. This study reports the synthesis, characterization, and performance of a visible-active ternary nanocomposite, Cu₄O₃/ZrO₂/TiO₂, prepared hydrothermally alongside its binary (Cu₄O₃/ZrO₂) and rutile TiO₂ counterparts. XRD, FT-IR, SEM-EDX, UV-Vis, and PL analyses confirm a heterostructured architecture with a narrowed optical bandgap of 2.91 eV, efficient charge separation, and a mesoporous nanosphere-in-matrix morphology. Photocatalytic tests conducted under midsummer sunlight reveal that the ternary catalyst removes 91.41% of 40 ppm EY-3RS within 100 min, markedly surpassing the binary catalyst (86.65%) and TiO₂ (81.48%). Activity trends persist across a wide range of operational variables, including dye concentrations (20–100 ppm), catalyst dosages (10–40 mg), pH levels (3–11), and irradiation times (up to 100 min). The material retains ≈ 93% of its initial efficiency after four consecutive cycles, evidencing good reusability. This work introduces the first nanophotocatalytic strategy for EY-3RS degradation and underscores the promise of multi-oxide heterojunctions for solar-driven remediation of colored effluents. Full article

Novel AB-Polybenzimidazole (AB-PBI)/TiO₂ nanocomposite membranes have been prepared using a synthetic green chemistry approach. Modified Eaton’s reagent (methansulfonic acid/P₂O₅) was used as both reaction media for microwave-assisted synthesis of AB-PBI and as an efficient dispersant of partially agglomerated titanium dioxide powders. Composite membranes of 80 µm thickness have been prepared by a film casting approach involving subsequent anti-solvent inversion in order to obtain porous composite membranes possessing high sorption capacity. The maximal TiO₂ filler content achieved was 20 wt.% TiO₂ nanoparticles (NPs). Titania particles were green synthesized (using a different content of Mentha Spicata (MS) aqueous extract) by hydrothermal activation (150 °C), followed by thermal treatment at 400 °C. The various methods such as powder X-ray diffraction and Thermogravimetric analyses, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and Energy-dispersive X-ray spectroscopy, Electronic paramagnetic resonance, Scanning Electron Microscopy and Transmission Electron Microscopy have been used to study the phase and surface composition, structure, morphology, and thermal behavior of the synthesized nanocomposite membranes. The photocatalytic ability of the so-prepared AB-Polybenzimidazole/bio-TiO₂ membranes was studied for decolorization of Reactive Black 5 (RB5) as a model azo dye pollutant under UV light illumination. The polymer membrane in basic form, containing TiO₂ particles, was obtained with a 40 mL quantity of the MS extract, exhibiting the highest decolorization rate (96%) after 180 min of UV irradiation. The so-prepared AB-Polybenzimidazole/TiO₂ samples have a powerful antibacterial effect on E. coli when irradiated by UV light. Full article

Advanced oxidation process based on heterogeneous activation of peroxymonosulfate (PMS) has received significant attention in wastewater remediation. Herein, a facile and effective electrochemical method was introduced in a tungsten sulfide (WS₂)-activated PMS process for the removal of a typical azo dye Acid Orange 7 (AO7) in aqueous solution. It was found that the electrochemical activation could remarkably promote the removal of organic pollutants by coupling with WS₂/PMS system. The elimination of AO7 in the electro-assisted WS₂-activated PMS (E/WS₂/PMS) system achieved 95.8% of AO7 removal in 30 min, with the optimal conditions of 1.0 g/L WS₂, 1.0 mM PMS, current density of 1.0 mA/cm² and initial pH of 6.5. Based on quenching experiments and EPR techniques, mechanistic studies confirmed that hydroxyl radical (^•OH) and singlet oxygen (¹O₂) are the primary reactive oxygen species for the oxidation of pollutants. In addition, the influences of pH, WS₂ dosage, PMS concentration, current density, common anions and humic acid on the AO7 removal are also investigated in detail. Furthermore, the system exhibited resistance to aqueous matrices, verifying the accepted applicability in real water (i.e., Yangtze River water and Shahu Lake water). In summary, this study demonstrates a green system for the effective removal of contaminants in water, holding significant implications for practical application. Full article

Textile wastewater containing dyes poses significant environmental hazards. Advanced oxidative processes, especially the heterogeneous photo-Fenton process, are effective in degrading a wide range of contaminants due to high conversion rates and ease of catalyst recovery. This study evaluates the heterogeneous photodegradation of the azo dyes Acid Red 18 (AR18), Acid Red 66 (AR66), and Orange 2 (OR2) using magnetite as a catalyst. The magnetic catalyst was synthesized via a hydrothermal process at 150 °C. Experiments were conducted at room temperature, investigating the effect of catalyst dosage, pH, and initial concentrations of H₂O₂ and AR18 dye. Kinetic and thermodynamic studies were performed at 25, 40, and 60 °C for the three azo dyes (AR18, AR66, and OR2) and the effect of the dye structures on the degradation efficiency was investigated. At 25 °C for 0.33 mmolL⁻¹ of dye at pH 3.0, using 1.4 gL⁻¹ of the catalyst and 60 mgL⁻¹ of H₂O₂ under UV radiation of 16.7 mWcm⁻², the catalyst showed 62.3% degradation for AR18, 79.6% for AR66, and 83.8% for OR2 in 180 min of reaction. The oxidation of azo dyes under these conditions is spontaneous and endothermic. The pseudo-first-order kinetic constants indicated a strong temperature dependence with an order of reactivity of the type OR2 > AR66 > AR18, which is associated with the molecular size, steric hindrance, aromatic conjugation, electrostatic repulsion, and nature of the acid–base interactions on the catalytic surface. Full article

Synthetic wastewater was treated in lab-scale constructed wetlands (CWs) in sequencing batch mode to evaluate roles of aquatic plants for removing an azo dye: Reactive Yellow 86 (RY86). Under hydraulic retention time (HRT) of 5 days, removal by unplanted CWs was less than 20% for RY86 of 10–50 mg/L. The CWs planted with cattail and papyrus demonstrated RY86 removal of 50–68% and 73–84%, respectively. For wastewater containing 50 mg/L RY86, removal in the unplanted CW was <12%, even under a 15 day HRT, although it was 22–71% in CWs planted with cattail and 34–81% in CWs planted with cattail, with increasing values under HRTs of 1 day to 15 days. Both cattail and papyrus grew well, extending their roots in the CWs for 90 days. RY86-decolorizing microorganisms were detected in CW effluent. Overall, RY86 removal was positively correlated with evapotranspiration in the CWs, indicating the plant uptake as the main removal mechanism. Papyrus and cattail, especially the former, are suitable plants for CWs intended to treat RY86-containing wastewater. Full article

Photocatalysis, mainly using TiO₂ as a catalyst, has emerged as a promising method to address the issue of wastewater treatment. This study explores the enhanced photocatalytic activity of TiO₂ through the introduction of reduced graphene oxide (rGO) and cadmium sulfide (CdS) as selective metal dopants. The incorporation of rGO and CdS into the TiO₂ lattice aims to optimize its photocatalytic properties, including bandgap engineering, charge carrier separation, and surface reactivity. The unique combination of CdS and rGO with TiO₂ is expected to boost degradation efficiency and reduce the reliance on expensive and potentially harmful sensitizers. This experimental investigation involves the synthesis and characterization of TiO₂-based photocatalysts. The photocatalytic degradation of methyl orange (MO) and methylene blue (MB) was assessed under controlled laboratory conditions, studying the influence of metal dopants on degradation kinetics and degradation efficiency. Furthermore, the synthesized photocatalyst is characterized by advanced techniques, including BET, SEM, TEM, XRD, and XPS analyses. The degraded samples were analyzed by UV-Vis spectroscopy. Insights into the photoexcitation and charge transfer processes shed light on the role of metal dopants in enhancing photocatalytic performance. The results demonstrate the potential of a TiO₂-rGO-CdS-based photocatalyst in which 100% degradation was achieved within four hours for MO and six hours for MB, confirming efficient azo dye degradation. The findings contribute to understanding the fundamental principles underlying the photocatalytic process and provide valuable guidance for designing and optimizing advanced photocatalytic systems. Ultimately, this research contributes to the development of sustainable and effective technologies for removing azo dyes from various wastewaters, promoting environmental preservation and human well-being. Full article

The adsorption of copper ions and Reactive Red 120 azo dye (RR-120) as models of water pollutants on unmodified halloysite (H-NM), as well as halloysites modified with sulfuric acid (H-SA) and (3-aminopropyl)triethoxysilane (H-APTES), was investigated. The results showed that adsorption of both the adsorbates was pH-dependent and increased with the increase in halloysite dosage. The adsorption kinetics were evaluated and the results demonstrated that the adsorption followed the pseudo-second-order model. The adsorption isotherms of Cu(II) ions and RR-120 dye on the halloysites were described satisfactorily by the Langmuir model. The maximum adsorption capacities for the Cu(II) ions were 0.169, 0.236, and 0.507 mmol/g, respectively, for H-NM, H-SA, and H-APTES indicating that the NH₂-functionalization rather than the surface area of the adsorbents was responsible for the enhanced adsorption. The adsorption capacities for RR-120 dye were found to be 9.64 μmol/g for H-NM, 75.76 μmol/g for H-SA, and 29.33 μmol/g for H-APTES. The results demonstrated that APTES-functionalization and sulfuric acid activation are promising modifications, and both modified halloysites have good application potential for heavy metals as well as for azo dye removal. Full article

A novel approach to enhance the utilization of low-cost and sustainable chitosan for wastewater remediation is presented in this investigation. The study centers around the modification of chitosan beads using a deep eutectic solvent composed of choline chloride and urea at a molar ratio of 1:2, followed by treatment with sulfuric acid using an impregnation accessible methodology. The effectiveness of the modified chitosan beads as an adsorbent was evaluated by studying the removal of the azo dye Reactive Black 5 (RB5) from aqueous solutions. Remarkably, the modified chitosan beads demonstrated a substantial increase in adsorption efficiency, achieving excellent removal of RB5 within the concentration range of 25–250 mg/L, ultimately leading to complete elimination. Several key parameters influencing the adsorption process were investigated, including initial RB5 concentration, adsorbent dosage, contact time, temperature, and pH. Quantitative analysis revealed that the pseudo-second-order kinetic model provided the best fit for the experimental data at lower dye concentrations, while the intraparticle diffusion model showed superior performance at higher RB5 concentration ranges (150–250 mg/L). The experimental data were successfully explained by the Langmuir isotherm model, and the maximum adsorption capacities were found to be 116.78 mg/g at 298 K and 379.90 mg/g at 318 K. Desorption studies demonstrated that approximately 41.7% of the dye could be successfully desorbed in a single cycle. Moreover, the regenerated adsorbent exhibited highly efficient RB5 removal (80.0–87.6%) for at least five consecutive uses. The outstanding adsorption properties of the modified chitosan beads can be attributed to the increased porosity, surface area, and swelling behavior resulting from the acidic treatment in combination with the DES modification. These findings establish the modified chitosan beads as a stable, versatile, and reusable eco-friendly adsorbent with high potential for industrial implementation. Full article

Synthetic dyes, exceeding 100,000 types on the market and produced at a global scale of over 700,000 tons annually, are extensively used in the textile industry. This industry, a leading contributor to water contamination, relies on dyes like reactive, azo, anthraquinone, and triphenylmethane, resulting in substantial water usage and significant effluent generation. A significant modern challenge is the pollution caused by dye-mixed wastewater, releasing hazardous chemicals into water bodies and posing threats to ecosystems, plants, and human health. Traditionally, physicochemical techniques have addressed textile dye-containing wastewater, but their drawbacks, including cost, inefficiency, and potential secondary pollution, have steered attention towards biological alternatives. Utilizing microorganisms and enzymes, these biological methods, such as microbial cell enzyme immobilization, the biofilm technique, bioreactors, biofuel/bioelectricity production, and genetic engineering, have emerged as promising, cost-effective, and environmentally friendly solutions for efficient dye removal from wastewater. This review paper specifically highlights advanced biological techniques and emphasizes their efficacy in addressing the challenges posed by synthetic textile dyes. Through a systematic review of recent research papers, published results, and observations, this review paper provides insights into emerging biological treatment strategies for effectively removing synthetic textile dyes and contaminants from wastewater. Full article

To fully harness the potential of laccase in the efficient decolorization and detoxification of single and mixed dyes with diverse chemical structures, we carried out a systematic study on the decolorization and detoxification of single and mixed dyes using a crude laccase preparation obtained from a white-rot fungus strain, Pleurotus eryngii. The crude laccase preparation showed efficient decolorization of azo, anthraquinone, triphenylmethane, and indigo dyes, and the reaction rate constants followed the order Remazol Brilliant Blue R > Bromophenol blue > Indigo carmine > New Coccine > Reactive Blue 4 > Reactive Black 5 > Acid Orange 7 > Methyl green. This laccase preparation exhibited notable tolerance to SO₄²⁻ salts such as MnSO₄, MgSO₄, ZnSO₄, Na₂SO₄, K₂SO₄, and CdSO₄ during the decolorization of various types of dyes, but was significantly inhibited by Cl⁻ salts. Additionally, this laccase preparation demonstrated strong tolerance to some organic solvents such as glycerol, ethylene glycol, propanediol, and butanediol. The crude laccase preparation demonstrated the efficient decolorization of dye mixtures, including azo + azo, azo + anthraquinone, azo + triphenylmethane, anthraquinone + indigo, anthraquinone + triphenylmethane, and indigo + triphenylmethane dyes. The decolorization kinetics of mixed dyes provided preliminary insight into the interactions between dyes in the decolorization process of mixed dyes, and the underlying reasons and mechanisms were discussed. Importantly, the crude laccase from Pleurotus eryngii showed efficient repeated-batch decolorization of single-, two-, and four-dye mixtures. This crude laccase demonstrated high stability and reusability in repeated-batch decolorization. Furthermore, this crude laccase was efficient in the detoxification of different types of single dyes and mixed dyes containing different types of dyes, and the phytotoxicity of decolorized dyes (single and mixed dyes) was significantly reduced. The crude laccase efficiently eliminated phytotoxicity associated with single and mixed dyes. Consequently, the crude laccase from Pleurotus eryngii offers significant potential for practical applications in the efficient decolorization and management of single and mixed dye pollutants with different chemical structures. Full article

In this study, the facile removal of the chromium-complex-based reactive azo dye C. I. Reactive Black 8 (RB8) from model wastewaters by the co-action of alternative sorbents—biochar (BC) and bentonite (BT)—with ionic liquids such as benzalkonium chloride (BAC) or Aliquat 336 (A336) was studied. The experiments using model RB8-containing wastewater proved that the co-action of BAC with BC is the most promising method of RB8 separation from wastewater containing 1 g L⁻¹ of RB8 dye. The application of 2 g L⁻¹ BC in co-action with 1.5 g L⁻¹ BAC or 1 g L⁻¹ BT in co-action with 2 g L⁻¹ BAC enables the removal of more than 98% of contaminant RB8 after 30 min of action. Similar removal efficiency (RE) was achieved using 40 g L⁻¹ of powdered activated carbon (PAC) after 180 min of action. To reach the same RE using real RB8-containing wastewater, a four times higher dose of BC and a four times higher dose of BAC per gram of removed RB8 were required. The proposed mechanism of RB8 removal by the co-action of alternative sorbents with BAC comprises a parallel effect of (i) sorption, (ii) the formation of less polar ion pairs accompanied by their sorption on an alternative sorbent and (iii) the separation of used alternative sorbents covered with ion pairs. The removal efficiency of organic contaminant(s) from both model and real wastewater was evaluated by VIS spectroscopy applying the Lambert–Beer law and by the determination of chemical oxidation demand (COD) and/or adsorbable organically bound halogen (AOX) parameters. Full article

This study investigates the biodegradation of Reactive Red 141 (RR 141), an azo dye prevalent in the textile industry, by bacteria isolated from activated sludge in a textile effluent treatment plant. RR 141, characterized by nitrogen–nitrogen double bonds (-N=N-), contributes to environmental issues when improperly disposed of in textile effluents, leading to reduced oxygen levels in water bodies, diminished sunlight penetration, and the formation of potentially carcinogenic and mutagenic aromatic amines. This research focuses on identifying bacteria from activated sludge with the potential to decolorize RR 141. Microbiological identification employs MALDI-TOF-MS, known for its precision and rapid identification of environmental bacteria, enhancing treatment efficiency. Results highlight Bacillus thuringiensis and Kosakonia radicincitans as the most promising strains for RR 141 decolorization. Analysis of micro-organisms in activated sludge and database exploration suggests a correlation between these strains and the decolorization process. It is worth noting that this is the first report on the potential use of K. radicincitans for azo dye decolorization. Three distinct culture media—BHI, MSG, and MS—were assessed to investigate their impact on RR 141 decolorization. Notably, BHI and MSG media, incorporating a carbon source, facilitated the bacterial growth of both tested species (B. thuringiensis and K. radicincitans), a phenomenon absent in the MS medium. This observation suggests that the bacteria exhibit limited capability to utilize RR 141 dye as a carbon source, pointing towards the influence of the culture medium on the discoloration process. The study evaluates performance kinetics, decolorization capacity through UV-VIS spectrophotometry, potential degradation pathways via HPLC-MS analysis, phytotoxicity, and enzymatic activity identification. B. thuringiensis and K. radicincitans exhibit potential in decolorizing RR141, with 38% and 26% removal individually in 120 h. As a consortium, they achieved 36% removal in 12 h, primarily through biosorption rather than biodegradation, as indicated by HPLC-MS analyses. In conclusion, the research emphasizes the importance of exploring bacteria from activated sludge to optimize azo dye degradation in textile effluents. B. thuringiensis and K. radicincitans emerge as promising candidates for bioremediation, and the application of MALDI-TOF-MS proves invaluable for rapid and precise bacteria identification. Full article