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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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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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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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The anti-cancer drug Flutamide (FLUT) is widely used and is of great environmental concern. The solar photo-Fenton (SPF) process can be an effective treatment for the removal of this type of micropollutant. The use of a single addition of 5 mg L-1 of Fe2+ and 50 mg L-1 of H2O2 achieved 20% primary degradation and only 3.05% mineralization. By using three additions of 5 mg L-1 Fe2+, with an initial H2O2 concentration of 150 mg L-1, 58% primary degradation was achieved, together with 12.07% mineralization. Consequently, thirteen transformation products (TPs) were formed. The SPF process was further combined with adsorption onto avocado seed activated carbon (ASAC) as an environmentally friendly approach for the removal of remained FLUT and the TPs. Doehlert design was used to assess the behavior of 13 TPs by optimizing the contact time and the adsorbent mass load. The optimal conditions for removal of FLUT and the TPs were 14 mg of ASAC and a contact time of 40 min. Remained FLUT and the TPs were totally removed using the adsorption process. The mechanisms of adsorption of FLUT and the TPs were strongly influenced by their polarity and π-π interactions of the TPs onto ASAC.

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Flutamide (FLUT) is a non-steroidal drug mainly used in the treatment of prostate cancer and has been detected in the aquatic environment at ng L-1 levels. The environmental fate and effects of FLUT have not yet been studied. Conventional treatment technologies fail to completely remove pharmaceuticals, so the solar photo-Fenton process (SPF) has been proposed as an alternative. In this study, the degradation of FLUT, at two different initial concentrations in ultra-pure water, was carried out by SPF. The initial SPF conditions were pH0 5, [Fe2+]0 = 5 mg L-1, and [H2O2]0 = 50 mg L-1. Preliminary elimination rates of 53.4% and 73.4%. The kinetics of FLUT degradation could be fitted by a pseudo-first order model and the kobs were 6.57 × 10-3 and 9.13 × 10-3 min-1 t30W and the half-life times were 95.62 and 73.10 min t30W were achieved for [FLUT]0 of 5 mg L-1 and 500 µg L-1, respectively. Analysis using LC-QTOF MS identified thirteen transformation products (TPs) during the FLUT degradation process. The main degradation pathways proposed were hydroxylation, hydrogen abstraction, demethylation, NO2 elimination, cleavage, and aromatic ring opening. Different in silico (quantitative) structure-activity relationship ((Q)SAR) freeware models were used to predict the toxicities and environmental fates of FLUT and the TPs. The in silico predictions indicated that these substances were not biodegradable, while some TPs were classified near the threshold point to be considered as PBT compounds. The in silico (Q)SAR predictions gave positive alerts concerning the mutagenicity and carcinogenicity endpoints. Additionally, the (Q)SAR toolbox software provided structural alerts corresponding to the positive alerts obtained with the different mutagenicity and carcinogenicity models, supporting the positive alerts with more proactive information.

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Natural effluents with marked variation in their chemical composition over decomposition time in the matrix from which they are generated have a complex composition and are not totally known in most cases. Landfill leachate can be considered an effluent with complex composition, requiring imminent and more comprehensive studies on organic load degradation. Such complexity of numerous organic compounds (most of them recalcitrant humic and fulvic substances) demands a large number of kinetic equations to satisfactorily describe the temporal evolution of such conversion. Thereby, this work aims to study a kinetic approach grounded on previously consolidated chemical reactions of radical generation through the photo-Fenton mechanism. A molar balance was developed for each species in a batch photo-Fenton process and the resulting ordinary differential equations were numerically solved in MATLABTM. The kinetic model satisfactorily described an organic load conversion of the effluent under the various experimental conditions studied herein. Experimental trends could be represented by a free-radical mechanism and a degradation rate equation of first order for organic carbon, hydroxyl radical and H+. The model fittings revealed a hydroxyl radical/organic carbon stoichiometric ratio of 2:1. The kinetic study has confirmed the importance of pH levels for the reaction medium, and indicated that degradation rate depends on the medium organic composition, which provided an exponential function of conversion for the degradation rate coefficient. The model simulations corroborated the positive effect of sunlight on the radical generation through [Formula: see text] decomposition reaction with a rate coefficient in the range 4 × 10-3-2 × 10-1 s-1.

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The use of the solar photo-Fenton process for water treatment requires monitoring of the main conditions, especially the total dissolved iron concentration and the consumption of hydrogen peroxide. In this study, a new methodology using the PhotoMetrixPRO application was validated for rapid monitoring of total dissolved iron and hydrogen peroxide concentrations, and was tested in the solar photo-Fenton process. A comparison was made between the results obtained using a reference spectrophotometric method and the PhotoMetrixPRO application employing a portable device. Both methods were validated in terms of linearity, sensitivity, precision, robustness, and matrix effects. The degree of dispersion between the series of measurements obtained using UV-vis and portable device tool was low and was in compliance with the established Brazilian and ICH validation criteria. Additionally, PhotoMetrixPRO enabled the use of a smaller sample volume. The total volume generated of each sample is 1 mL, reducing 6 and 10 times the wastes produced in different validated methods. These results evidencing that the miniaturization can provide positive advantages in terms of simplicity, cost effectiveness, and less environmental impact. PhotoMetrixPRO offers significant advantages including rapid analysis, smaller sample volumes, and greater portability and accessibility.

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RESUMO Neste trabalho foi avaliado o processo foto-Fenton solar mediado por ferrioxalato como tratamento primário de um efluente têxtil bruto (E1) e como um processo de polimento, após processo de lodos ativados (E2). Por um ano, ao menos uma vez por mês, a eficiência de descoloração e o comportamento dos sólidos foram avaliados sob condições naturais de radiação, temperatura e características dos efluentes. As condições operacionais foram as seguintes: 50 mg L-1 de ferro, pH 5, 525 mg L-1 de H2O2, administrados em dosagens decrescentes. O oxalato foi adicionado na razão molar de 1:3 [Fe+3:(C2O4)-2]. A descoloração máxima de E1 foi de 67% para intensidade de radiação de 690 W m-2; já a de E2 foi de 95% para intensidade de 620 W m-2. Houve considerável aumento na turbidez e nos sólidos suspensos em função da precipitação do ferro e de sua ação coagulante. A degradação do complexante durante o processo no E2 em dias ensolarados provocou elevada sedimentabilidade dos sólidos do efluente final, resultando em um sobrenadante clarificado, o que não ocorreu em dias nublados.

ABSTRACT This work evaluates the solar photo-Fenton process mediated by ferrioxalate as a primary treatment of raw textile effluent (E1) and as a polishing step, after active sludge process (E2). For a year, at least once a month, the color removal's efficiency and solids' behavior in the oxidative process treatment were analyze under natural conditions of light, temperature and effluents characteristics. The operational parameters values were: 50 mg L-1 iron, pH 5, 525 mg L-1 H2O2, introduced in decreasing doses. The oxalate was added at the molar ratio of 1:3 [Fe+3:(C2O4)-2]. The color removal of E1 was 60% for 690 W m-2 of radiation intensity and 95% for 620 W m-2 intensity to E2. Considerable increases were observed in turbidity and suspended solids due to the iron precipitation and the consequent coagulant action. In sunny days, the complex degradation in E2 resulted in high settle ability of solids in the final effluent, resulting in a clear supernatant. This has not happened in cloudy days.

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Scarcity of water and concerns about the ecotoxicity of micro-contaminants are driving an interest in the use of advanced tertiary processes in wastewater treatment plants. However, the life cycle environmental implications of these treatments remain uncertain. To address this knowledge gap, this study evaluates through life cycle assessment the following four advanced process options for removal of micro-contaminants from real effluents: i) solar photo-Fenton (SPF) operating at acidic pH; ii) acidic SPF coupled with nanofiltration (NF); iii) SPF operating at neutral pH; and iv) neutral SPF coupled with NF. The results show that acidic SPF coupled with NF is the best option for all 15 impacts considered. For example, its climate change potential is almost three times lower than that of the neutral SPF process (311 vs 928 kg CO2 eq./1000 m3 of treated effluent). The latter is the worst option for 12 impact categories. For the remaining three impacts (acidification, depletion of metals and particulate matter formation), acidic SPF without NF is least sustainable; it is also the second worst option for seven other impacts. Neutral SPF with NF is the second worst technology for climate change, ozone and fossil fuel depletion as well as marine eutrophication. In summary, both types of SPF perform better environmentally with than without NF and the acidic SPF treatment is more sustainable than the neutral version. Thus, the results of this work suggest that ongoing efforts on developing neutral SPF should instead be focused on further improvements of its acidic equivalent coupled with NF. These results can also be used to inform future development of policy related to the removal of micro-contaminants from wastewater.

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The Photo-Fenton-like (PF-like) process with minute Fe(III) concentrations and the Hydrogen Peroxide Photolysis (HPP), using Xe-lamp or solar light as sources of irradiation, were efficiently applied to eliminate the herbicide 2,4-D from water. PF-like experiments concerning ferric and H2O2 concentrations of 0.6 mg L-1 and 20 mg L-1 respectively, using Xenon lamps (Xe-lamps) as a source of irradiation and 2,4-D concentrations of 10 mg L-1 at pH 3.6, exhibited complete 2,4-D degradation and 77% dissolved organic carbon (DOC) removal after 30 min and 6 h of irradiation respectively whereas HPP (in absence of ferric ions) experiments showed a 2,4-D reduction and DOC removal of 90% and 7% respectively after 6 h of irradiation. At pH 7.0, HPP process achieved a 2,4-D abatement of approximately 75% and a DOC removal of 4% after 6 h. PF-like exhibited slightly improved 2,4-D and DOC removals (80% and 12% respectively) after the same irradiation time probably due to the low pH reduction (from 7.0 to 5.6). Several chlorinated-aromatic intermediates were identified by HPLC-MS. These by-products were efficiently removed by PF at pH 3.6, whereas at neutral PF-like and acid or neutral HPP, they were not efficiently degraded. With natural solar light irradiation, 10 and 1 mg L-1 of 2,4-D were abated using minor H2O2 concentrations (3, 6, 10 and 20 mg L-1) and iron at 0.6 mg L-1 in Milli-Q water. Similar results to Xe-lamp experiments were obtained, where solar UV-B + A light H2O2 photolysis (HPSP) and solar photo-Fenton-like (SPF-like) played an important role and even at low H2O2 and ferric concentrations of 3 and 0.6 mg L-1 respectively, 2,4-D was efficiently removed at pH 3.6. Simulated surface water at pH 3.6 containing 1 mg L-1 2,4-D, 20 mg L-1 H2O2 and 0.6 mg L-1 Fe(III) under natural sunlight irradiation efficiently removed the herbicide and its main metabolite 2,4-DCP after 30 min of treatment while at neutral pH, 40% of herbicide degradation was achieved. In the case of very low iron concentrations (0.05 mg L-1) at acid pH, 150 min of solar treatment was required to remove 2,4-D.

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Solar photo-Fenton represents an innovative and low-cost option for the treatment of recalcitrant industrial wastewater, such as the textile wastewater. Textile wastewater usually shows high acute toxic and variability and may be composed of many different chemical compounds. This study aimed at optimizing and validating solar photo-Fenton treatment of textile wastewater in a semi-pilot compound parabolic collector (CPC) for toxicity removal and wastewater reclamation. In addition, treated wastewater reuse feasibility was investigated through pilot tests. Experimental design performed in this study indicated optimum condition for solar photo-Fenton reaction (20 mg L-1 of Fe2+ and 500 mg L-1 of H2O2; pH 2.8), which achieved 96 % removal of dissolved organic carbon (DOC) and 99 % absorbance removal. A toxicity peak was detected during treatment, suggesting that highly toxic transformation products were formed during reaction. Toxic intermediates were properly removed during solar photo-Fenton (SPF) treatment along with the generation of oxalic acid as an ultimate product of degradation and COS increase. Different samples of real textile wastewater were treated in order to validate optimized treatment condition with regard to wastewater variability. Results showed median organic carbon removal near 90 %. Finally, reuse of treated textile wastewater in both dyeing and washing stages of production was successful. These results confirm that solar photo-Fenton, as a single treatment, enables wastewater reclamation in the textile industry. Graphical abstract Solar photo-Fenton as a revolutionary treatment technology for "closing-the-loop" in the textile industry.

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The solar photo-Fenton degradation of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) in aqueous solution at a natural pH (pH = 5) using ferrioxalate as iron source was investigated. The kinetic model proposed and validated in a previous contribution was used to predict the reactants concentrations during the oxidation process in a non-concentrating pilot-plant solar reactor. The effects of hydrogen peroxide to 2,4-D initial concentration ratios (R), temperature, and radiation levels were studied. Furthermore, the spectral UV/visible and broadband solar radiation fluxes incident on the reactor window were evaluated by the Simple Model for the Atmospheric Radiative Transfer of Sunshine (SMARTS2) code. The complete destruction of 2,4-D and its main intermediate 2,4-dichlorophenol (2,4-DCP) was achieved in all the experimental runs in only 90 and 120 min of reaction, respectively. In agreement with these results, a reduction of toxicity in the system (expressed as % of inhibition of Vibrio fischeri) for longer times to 90 min of reaction was attained. It is important to emphasize the good agreement between kinetic model results and experimental data obtained.

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