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This is the first record on literature to use biochar as support for CoFe2O4 to applicate and evaluate it as photocatalyst for degradation of organic pollutants. The support was verified by XRD, FT-IR, SEM, EDS and band gap. Composites CFO1BQ3, CFO1BQ1, and CFO3BQ1 showed 100% degradation in 60 min. This outstanding performance can be related to the drop in band gap energy and recombination rate of e¯/h + . The composites showed better efficiency when compared to pure CoFe2O4 (∼78%). This might be associate to the fact that biochar has a high concentration of phenolic, hydroxyl and carboxylic functional groups on its surface. In this reaction h+, O2•-, and •OH were the reactive species involved in the degradation. The toxicity of ponceau was tested before and after the treatment, through biochemical biomarkers in Danio rerio fish. In general, the treatment proved to be efficient in reducing ponceau toxicity in D. rerio fish.

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Productive activities such as pig farming are a fundamental part of the economy in Mexico. Unfortunately, because of this activity, large quantities of wastewater are generated that have a negative impact in the environment. This work shows an alternative for treating piggery wastewater based on advanced oxidation processes (Fenton and solar photo Fenton, SPF) that have been probed successfully in previous works. In the first stage, Fenton and SPF were carried out on a laboratory scale using a Taguchi L9-type experimental design. From the statistical analysis of this design, the operating parameters: pH, time, hydrogen peroxide concentration [H2O2], and iron ferrous concentration [Fe2+] that maximize the response variables: Chemical Oxygen Demand (COD), Total Organic Carbon (TOC), and color were chosen. From these, a cascade forward neural network was implemented to establish a correlation between data from the variables to the physicochemical parameters to be measure being that a great fit of the data was obtained having a correlation coefficient of 0.99 which permits to optimize the pollutant degradation and predict the removal efficiencies at pilot scale but with a projection to a future industrial scale. A relevant result, it was found that the optimal values for maximizing the removal of physicochemical parameters were pH = 3, time = 60 min, H2O2/COD = 1.5 mg L-1, and H2O2/Fe2+ = 2.5 mg L-1. With these conditions degradation percentages of 91.44%, 47.14%, and 97.89% for COD, TOC, and color were obtained from the Fenton process, while for SPF the degradation percentage increased moderately. From the ANN analysis, the possibility to establish an intelligent system that permits to predict multiple results from operational conditions has been achieved.

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Epoxiconazole (EPO) is classified as a persistent organic pollutant due to its ability to persist in the environment for prolonged periods. Its degradation is pivotal in mitigating its environmental impact. This investigation focuses on assessing the degradation of EPO using various methodologies, namely Fenton, photo-Fenton, solar photo-Fenton, and solar photolysis, conducted in both Milli-Q water and groundwater. These experiments encompassed evaluations at both the standard pH typically used in photo-Fenton reactions and the natural pH levels inherent to the respective aqueous environments. Additionally, EPO degradation products were analyzed after a 60-min reaction. Notably, in systems utilizing groundwater, the inclusion of additional iron was unnecessary, as the naturally occurring iron content in the groundwater facilitated the intended processes. Specifically, in Milli-Q water, solar photo-Fenton demonstrated an EPO degradation efficiency of 97%. Furthermore, the substitution of Milli-Q water with groundwater in Fenton-like processes did not significantly affect the efficacy of EPO degradation. These findings underscore the potential of solar photo-Fenton as an economically viable and environmentally sustainable strategy for EPO degradation.

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Azo dyes, widely used in the textile industry, contribute to effluents with significant organic content. Therefore, the aim of this work was to synthesize cobalt ferrite (CoFe2O4) using the combustion method and assess its efficacy in degrading the azo dye Direct Red 80 (DR80). TEM showed a spherical structure with an average size of 33 ± 12 nm. Selected area electron diffraction and XRD confirmed the presence of characteristic crystalline planes specific to CoFe2O4. The amount of Co and Fe metals were determined by ICP-OES, indicating an n(Fe)/n(Co) ratio of 2.02. FTIR exhibited distinct bands corresponding to Co-O (455 cm-1) and Fe-O (523 cm-1) bonds. Raman spectroscopy detected peaks associated with octahedral and tetrahedral sites. For the first time, the material was applied to degrade DR80 in an aqueous system, with the addition of persulfate. Consistently, within 60 min, these trials achieved nearly 100% removal of DR80, even after the material had undergone five cycles of reuse. The pseudo-second-order model was found to be the most fitting model for the experimental data (k2 = 0.07007 L mg-1 min-1). The results strongly suggest that degradation primarily occurred via superoxide radicals and singlet oxygen. Furthermore, the presence of UV light considerably accelerated the degradation process (k2 = 1.54093 L mg-1 min-1). The material was applied in a synthetic effluent containing various ions, and its performance consistently approached 100% in the photo-Fenton system. Finally, two degradation byproducts were identified through HPLC-MS/MS analysis.

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This work aimed to investigate the impact of hydrogen peroxide (HP) punctual dosage on paracetamol (PCT) degradation, through Fenton and photo-Fenton processes under near-neutral pH conditions, using ferrioxalate and artificial sunlight. The assays were performed using a D-optimal experimental design, to statistically evaluate the influence of radiation (ON or OFF), HP concentration (94.5-756 mg L-1), and HP dosage (YES or NO), on PCT conversion. The optimal conditions determined from the study were: HP = 378 mg L-1, DOS = YES, and RAD = ON, achieving a predicted PCT conversion of 99.68% in 180 min. This result obtained from the model was very close to the experimental one (98.80%). It was verified that HP dosage positively influenced the iron catalytic cycle since higher Fe2+ concentrations were reached at shorter reaction times, accelerating not only PCT conversion but also its by-products hydroquinone and 1,4-benzoquinone, leading to better performances of Fenton and photo-Fenton reactions. Under optimal conditions and employing real water matrices (an artificial matrix with inorganic anions, a real groundwater sample, and a synthetic industrial wastewater), HP dosage demonstrated the ability to mitigate the negative effects caused by the content of different ions and other organic compounds and significantly improve HP consumption in challenging wastewater conditions.

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In this work, complete elimination of Escherichia coli and Salmonella typhimurium was achieved in 120 min using a heterogeneous photo-Fenton process under sunlight at pH 6.5 in distilled water. A face-centered composite central design 22 with one categoric factor and three replicates at the central point was used to evaluate the effect of iron (III) oxide concentration (0.8-3.4 mg L-1), H2O2 (2-10 mg L-1), and the type of iron oxide phase (maghemite and hematite) on the inactivation of both bacteria. The results showed that the amount of catalyst, H2O2 concentration and their interaction were significant factors (p < 0.05) in the elimination of the microorganisms. Thus, under the best conditions (3.4 mg L-1 of iron (III) oxide and 10 mg L-1 of H2O2) in the experimental ranges, complete inactivation of E. coli and S. typhimurium was achieved (6-log reduction) in 120 min using the photo-Fenton treatment with both iron-oxide phases. Furthermore, the photocatalytic elimination of both bacteria by the photo-Fenton process using hematite and maghemite in secondary-treated wastewater effluent was performed obtaining slower inactivation rates (1.2-5.9 times) than in distilled water due to the matrix effect of the effluent from a wastewater treatment plant. Nevertheless, the process continued to be effective in the effluent, achieving complete bacterial elimination in 150 min using the hematite phase. Additionally, the SEM images of the bacterial cells showed that the heterogeneous photo-Fenton treatment generated permanent and irreversible cell damage, resulting in complete cell death.

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In this work, a novel support for an iron-based catalyst was prepared and employed for Ponceau 4R degradation by photo-Fenton reaction. To this, poultry waste was used for producing char, which was subsequently used to prepare the Fe2O3/Char composite. Process parameters, including catalyst dosage, pH, and hydrogen peroxide concentration, were investigated. The characterization analysis indicated that the textural properties of the composite were improved after impregnation with Fe2O3. The composite exhibited excellent catalytic activity, achieving a decolorization efficiency of 97% at 45 min and 81.06% organic carbon removal at 300 min. In addition, the material showed acceptable performance after four consecutive cycles. Furthermore, a scavenger test was performed to investigate the major reactive species involved in the Ponceau 4R oxidation, and a plausible mechanism for the respective reaction was projected. Therefore, the results of this research demonstrate that this material can be used as a potential catalyst for the abatement of dyed molecules from wastewater.

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Natural zeolite is a widely used material with excellent environmental cleaning performance, especially in water and wastewater treatment. Natural zeolite (Zini) calcined by CO2-laser radiation (ZL) was tested as a catalyst for the photodegradation and the adsorption of industrial azo dye Lanasol Yellow 4G (LY4G) in water. Morphology, chemical structure, and surface composition of Zini and ZL were analyzed by XRD, SEM, EDS, and XPS. UV/Visible spectrophotometry was used to evaluate the photocatalytic activity of Zini and ZL. The photocatalytic activity of the studied zeolites was associated with the presence of Fe oxides in their composition. Laser-treated natural zeolite showed higher efficiency as a photocatalyst compared to untreated natural zeolite.

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Antibiotics may induce super-resistant bacteria if they are available in the environment. Therefore, the removal of aqueous nitrofurantoin (NFT), and more importantly, the removal of the remaining antimicrobial activity after treatment, by the photo-Fenton process, was herein studied. Degradation experiments were performed according to an experimental design (0.5% error; factors: concentrations of NFT, Fe3+, and H2O2). Degradation conditions were: 20 mg NFT L-1, 10 mg Fe3+ L-1, and 170 mg H2O2 L-1. Fixed parameters were: 100 mL of the NFT solution, pH 2.5, 15-min stirring, and 25.0 ± 0.5°C. The initial rate constant (k0) and the maximum oxidation capacity (MOC) of the system were 0.61 min-1 and 100%, respectively (R2 = 0.986). 97% of the NFT and 93% of the organic carbon initially present were removed. Five degradation products (DPs) were detected by HPLC-MS and their endpoints estimated by the ECOSAR (ECOlogical Structure-Activity Relationships) 2.0 software. NFT and its DPs presented no toxicity towards Lactuca sativa. The antimicrobial activity (Escherichia coli) of NFT and/or DPs was completely removed in 15 min. Structures were proposed for the detected DPs. In short, the tested advanced oxidation technology (AOP), besides being capable of removing and mineralizing aqueous NFT in a short time, 15 min, also rendered the treated water biologically inactive (no ecotoxicity, no antimicrobial activity).

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It is known that copper can be used as catalyst in photo-Fenton-like process; however, there is a lack of information related with its use in the treatment of landfill leachate (LL) in solar photo-Fenton-like processes. Here, we studied the effect of the mass of a copper sheet, the pH of the solution, and the concentration of LL in the removal of the organic matter present in this water. Before the reaction with landfill leachate, the copper sheet used in the reaction was constituted by Cu+ and Cu2O, respectively. The results showed that in a volume of 0.5 L of a pretreated LL, the higher removal of organic matter resulted using a mass of 2.7 g of the copper sheet, a pH of solution of 5, and a concentration of LL of a 10%, obtaining a final value of C/C0 of chemical oxygen demand (COD) of 0.34, 0.54, 0.66, and 0.84 for concentrations of 25%, 50%, 75%, and 100%, respectively, and 0.0041, 0.0042, 0.0043, and 0.016 for concentration of 25%, 50%, 75%, and 100%, respectively, of C/C0 of humic acids. The photolysis on LL at its natural pH using solar UV removes very little humic acid and COD, going from 9.4 to 8.5 and 7.7 Abs254 for photolysis and UV + H2O2, obtaining 8.6 and 17.6% of removal, respectively, and 2.01 and 13.04% removal of COD, respectively. Copper sheet applied under Fenton-like conditions results in 65.9% removal and an increase of 0.2% for humic acid and COD, respectively. Removal using only H2O2 for Abs254 and COD was 11.95 and 4.3%, respectively. Raw LL produced a 29.1% inhibition of the biological activated sludge rate after the adjustment to pH 7 and the final process of inhibition was 0.23%.

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Two carbon dots (CD) with diameters of 4.9 ± 1.5 and 4.1 ± 1.2 nm were successfully synthesized through an acid ablation route with HNO3 or H2SO4, respectively, using Ilex paraguariensis as raw material. The CD were used to produce magnetite-containing nanocomposites through two different routes: hydrothermal and in situ. A thorough characterization of the particles by transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), dynamic light scattering (DLS), Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS) indicates that all nanomaterials have spherical-like morphology with a core-shell structure. The composition of this structure depends on the route used: with the hydrothermal route, the shell is composed of the CD, but with the in situ process, the CD act as nucleation centers, and so the iron oxide domains are in the shell. Regarding the photocatalytic mechanism for the degradation of methyl orange, the interaction between the CD and the magnetite plays an important role in the photo-Fenton reaction at pH 6.2, in which ligand-to-metal charge transfer processes (LTMCT) allow Fe2+ regeneration. All materials (100 ppm) showed catalytic activity in the elimination of methyl orange (8.5 ppm), achieving discoloration of up to 98% under visible irradiation over 400 nm in 7 h. This opens very interesting possibilities for the use of agro-industrial residues for sustainable synthesis of catalytic nanomaterials, and the role of the interaction of iron-based catalysts with organic matter in heterogeneous Fenton-based processes.

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This research studies the use of vinasse (VS) coming from Pisco and caffeic acid (Caa) from solid coffee waste as chelating agents of this process, to carry out a photo-Fenton process using UVc lamps of 254-nm wavelength for 60 min, at the natural pH of the landfill leachate (8.9). Without the chelating agent, there was a removal of UV 254 and COD of 54.2% and 54.7%, respectively, when the photo-Fenton reaction was carried out at pH 3; at pH 6, the removal of UV 254 and COD was 13.1% and 39.2%, respectively, and at pH 8.9, the elimination of UV 254 and COD was 10.8% and 16.1%, respectively. When Caa was used in the landfill leachate (LL) for the photo-catalytic processes carried out at pH 8.9, a removal of 24.1%, 43.0%, and 47.4% of UV 254 was obtained using 5 mg/L, 50 mg/L, and 100 mg/L of Caa. The removal of UV 254 was 27.3%, 30.7%, and 36.3% using 5 mg/L, 50 mg/L, and 100 mg/L of VS, respectively, and the removal of COD was 32.2%, 35.4%, and 39.2% using 5 mg/L, 50 mg/L, and 100 mg/L of VS, respectively. When Caa was used in the LL at pH 8.9, the concentration of total Fe went from 37.5 to 33.2, from 40.2 to 36.8, and from 45.2 to 42.1, using 5 mg/L, 50 mg/L, and 100 mg/L of caffeic acid, respectively. Using VS in the LL at pH 8.9, the concentration of total Fe along the run went from 35.1 to 32.2, from 39.4 to 34.8, and from 42.1 to 40.2, using 5 mg/L, 50 mg/L, and 100 mg/L of VS, respectively. As a result of these processes, it was noted that the use of Caa and VS increases the solubility of Fe at a higher pH.

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Several treatment strategies have been proposed to minimize the environmental impact of dairy wastewaters. However, their complex and variable composition makes it difficult to predict the degradation kinetics of organic compounds. In this study, we used a mathematical approach to describe the kinetics of total organic carbon degradation in real dairy wastewater by photo-Fenton oxidation. The reactions were conducted under different ultraviolet light intensities, pH, temperature and Fenton reagent concentrations, obtaining a maximum TOC removal of 90.84%. The kinetic model was developed based on well-established photo-Fenton reactions. The present approach considers that account that small and large molecules of unknown contaminants are present in the effluent, and the smaller molecules are consumed first. The specific degradation rate (kd) was considered as an exponential function of total organic carbon conversion, comprising this effect of molecular size distribution on the treatment process. Fitting of experimental data to model predictions provided mean R2 values of 0.843-0.953.

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The application of solar photo-Fenton as post-treatment of municipal secondary effluents (MSE) in developing tropical countries is the main topic of this review. Alternative technologies such as stabilization ponds and upflow anaerobic sludge blanket (UASB) are vastly applied in these countries. However, data related to the application of solar photo-Fenton to improve the quality of effluents from UASB systems are scarce. This review gathered main achievements and limitations associated to the application of solar photo-Fenton at neutral pH and at pilot scale to analyze possible challenges associated to its application as post-treatment of MSE generated by alternative treatments. To this end, the literature review considered studies published in the last decade focusing on CECs removal, toxicity reduction and disinfection via solar photo-Fenton. Physicochemical characteristics of effluents originated after UASB systems alone and followed by a biological post-treatment show significant difference when compared with effluents from conventional activated sludge (CAS) systems. Results obtained for solar photo-Fenton as post-treatment of MSE in developed countries indicate that remaining organic matter and alkalinity present in UASB effluents may pose challenges to the performance of solar advanced oxidation processes (AOPs). This drawback could result in a more toxic effluent. The use of chelating agents such as Fe3+-EDDS to perform solar photo-Fenton at neutral pH was compared to the application of intermittent additions of Fe2+ and both of these strategies were reported as effective to remove CECs from MSE. The latter strategy may be of greater interest in developing countries due to costs associated to complexing agents. In addition, more studies are needed to confirm the efficiency of solar photo-Fenton on the disinfection of effluent from UASB systems to verify reuse possibilities. Finally, future research urges to evaluate the efficiency of solar photo-Fenton at natural pH for the treatment of effluents from UASB systems.

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The analysis of chemical oxygen demand (COD) plays an important role in measuring water pollution, but it normally has a high ecological price. Advances in image acquisition and processing techniques enable the use of mobile devices for analytical purposes. Here, the PhotoMetrix PRO application was used for image acquisition and multivariate analysis. Statistical analysis showed no significant difference in the results compared to the standard method, with no adverse effect of the volume reduction. The cost of analysis and waste generation were reduced by one third, while the analysis time was reduced by one fifth. The miniaturized method was successfully employed in the analysis of several matrices and for the evaluation of advanced oxidation processes. The AGREE score was improved by 25% due to miniaturization. For these reasons, the miniaturized PhotoMetrix PRO method is a suitable option for COD analysis, being less hazardous to the environment due to reductions in the chemicals used and in waste generation.

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Paracetamol (PCT), also known as acetaminophen, is a drug used to treat fever and mild to moderate pain. After consumption by animals and humans, it is excreted through the urine to the sewer systems, wastewater treatment plants, and other aquatic/natural environments. It has been detected in trace amounts in effluents of wastewater plant treatments, sewage sludge, hospital wastewaters, surface waters, and drinking water. PCT can cause genetic code damage, oxidative degradation of lipids, and denaturation of protein in cells, and its toxicity has been well-proven in bacteria, algae, macrophytes, protozoan, and fishes. To avoid its harmful health problems over living beings, powerful Fenton and Fenton-based treatments as pre-eminent advanced oxidation processes (AOPs) have been developed because of the inefficient treatment by conventional treatments. This paper presents a comprehensive and critical review over the application of such Fenton technologies to remove PCT from natural waters, synthetic wastewaters, and real wastewaters. The characteristics and main results obtained using Fenton, photo-Fenton, electro-Fenton, and photoelectro-Fenton are described, making special emphasis in the oxidative action of the generated reactive oxygen species. Hybrid processes based on the coupling with ultrasounds, gamma radiation, photocatalysis, photoelectrocatalysis, zero-valent iron-activated persulfate, adsorption, and microbial fuel cells, are analyzed. Sequential treatments involving the initiation with plasma gliding arc discharge and post-biological process are detailed. Comparative results with other available AOPs are also described and discussed. Finally, 13 aromatic by-products and 9 short-linear aliphatic carboxylic acid detected during the PCT removal by Fenton and Fenton-based processes are reported, with the proposal of three parallel pathways for its initial degradation.

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Seven composites of iron oxide nanoparticles embedded in organic microparticles mediated by Cu(II) were synthesized using yerba mate (Ilex paraguariensis) dry leaf extract as precipitant, capping agent, and dispersant medium, using different Cu/Fe molar ratios. A thorough characterization of the particles by transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis-mass spectrometry (TGA-MS), Fourier transform infrared spectrometer (FTIR), and atomic absorption-spectrometry (AA) indicates that all materials have spheric-like morphology with nanoparticles composed by metal oxide phases embedded into organic microparticles. Interestingly, this organic matter is proposed to play an important role in the solids' photocatalytic activity in a photo-Fenton reaction, in which iron photo-leaching was elucidated, and a mechanism through ligand-to-metal charge transfer processes was proposed. All materials showed catalytic activity in the methyl orange elimination, achieving discolorations up to 96% in 2 h under UV irradiation at 375 nm. An experimental correlation between all samples' UV/Vis spectra and their performances for methyl orange discoloration was observed. This process opens a landscape very interesting for the use of agroindustrial residues for green synthesis of metal oxide nanomaterials and their use and understanding of organo-metallic systems participation in Fenton-based processes.

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In this study, a stochastic model was applied to investigate the degradation of landfill leachate by solar photo-Fenton processes. The coefficient of determination (R2) between experimental and predicted data ranged from 0.9958-0.9995. The optimal conditions for the initial phase (lasting 5-22 min) were high Fe2+ level, low pH level, and intermediate H2O2 level. For the second phase, optimal leachate degradation percentages were obtained by maintaining the pH, increasing H2O2, and decreasing Fe2+ to the lowest level. Determination of optimal reaction conditions (such as pH, Fe2+, and H2O2 values) for both degradation phases is of paramount importance for process scale-up. The major contribution of this study was the development of a tool that considers the effects of one or more reactions on organic carbon degradation. This was achieved by assessing the significance of the effects of experimental conditions on model parameters for the fast and slow steps of leachate degradation by advanced oxidation processes.

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This article presents a study on the degradation of a residual textile mixture composed of cationic surfactant cetyltrimethylammonium bromide (CTAB) and the remazol yellow gold RNL-150% and reactive blue BF-5G textile dyes. This was carried out by employing the photo-peroxidation and photo-Fenton processes in LED and UV-C photoreactors. The photo-Fenton process was the most efficient as regards the degradation of the CTAB and dye mixture, for both types of radiation. In the kinetic study, degradations of 99% were obtained in 180 min for the chromophore groups using both types of radiation. The degradation of the CTAB and aromatic groups was, meanwhile, an average of 25% when employing LED radiation. The behavior of the degradation reaction was pseudo-first-order. Toxicity tests indicated that the solutions were better able to grow seeds and bacteria after treatment with the photo-Fenton process, using both types of radiation. The photo-Fenton processes carried out by employing LED and UV-C photoreactors were able to degrade the CTAB and dye mixture, thus highlighting the efficiency of LED radiation when its power (three times smaller) is compared to that of UV-C radiation. This process, therefore, represents an alternative for use in textile wastewater treatment systems.

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Formation of oxygen-based free radicals from photochemical decomposition of hydrogen peroxide (H2O2) on Mars may be a key factor in the potential survival of terrestrial-like organisms on the red planet. Martian conditions that generate reactive oxygen species involve the decomposition of H2O2 at temperatures of around 278 K under relatively high doses of C-band ultraviolet radiation (UVC). This process is further amplified by the presence of iron oxides and perchlorates. Photosynthetic organisms exhibit a number of evolutionary traits that allow them to withstand both oxidative stress and UVC radiation. Here, we examine the effect of free radicals produced by the decomposition of H2O2 under emulated martian conditions on the viability of Scenedesmus dimorphus, a unicellular alga that is resistant to UVC radiation and varying levels of perchlorate and H2O2, both of which are present on Mars. Identification and quantification of free radicals formed under these conditions were performed with Electron Paramagnetic Resonance spectroscopy. These results were correlated with the viability of S. dimorphus, and the formation of oxygen-based free radicals and survival of the alga were found to be strongly dependent on the amount of H2O2 available. For H2O2 amounts close to those present in the rarefied martian environment, the products of these catalytic reactions did not have a significant effect on the algal population growth curve.

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