Open-access Fenton treatment of agro-industrial effluent

Tratamento Fenton para efluente agroindustrial

ABSTRACT

The increasing volume of waste has become a global concern, with agro-industrial residues, such as vinasse, standing out. Vinasse is a byproduct generated on a large scale by the sugarcane industry. Its continuous and uncontrolled use on soil can cause the leaching of minerals into water bodies and saturate the soil's water retention capacity. The Fenton process has gained prominence worldwide for treating complex effluents like vinasse due to its low cost, efficiency, and alignment with the United Nations Sustainable Development Goals (SDGs). In this study, the Fenton reaction was applied using statistical modeling, and the ideal reagent ratio of [Fe2+]:[H2O2] was determined to be 50%: 75%, achieving 78.14% chemical oxygen demand removal, 100% turbidity reduction, and significant decreases in nitrogen, phosphorus, potassium, and other contaminants. Treated vinasse also improved soil moisture and pH correction without causing leaching, thus enhancing nutrient retention and plant absorption.

Keywords:
advanced oxidative processes; fenton; vinasse; fertigation

RESUMO

O crescente volume de resíduos tem se tornado uma preocupação global, com destaque para os resíduos agroindustriais, como a vinhaça, um efluente gerado em grande escala pela indústria sucroalcooleira. Seu uso contínuo e descontrolado no solo pode causar lixiviação de minerais para corpos hídricos e saturar a capacidade de retenção de água do solo. O processo Fenton tem se consolidado mundialmente no tratamento de efluentes complexos como a vinhaça, devido ao seu baixo custo, eficácia e alinhamento com os Objetivos de Desenvolvimento Sustentável da ONU (ODS). Neste estudo, a reação de Fenton foi aplicada com modelagem estatística, e a proporção ideal de reagentes [Fe2+]:[H2O2] foi de 50%: 75%, alcançando remoção de 78,14% da DQO, 100% da turbidez e significativa redução de nitrogênio, fósforo, potássio e outros contaminantes. A vinhaça tratada também proporcionou aumento da umidade e correção do pH do solo, sem provocar lixiviação, favorecendo a retenção de nutrientes e sua absorção pelas plantas.

Palavras-chave:
processos oxidativos avançados; fenton; vinhaça; fertirrigação

INTRODUCTION

Ethanol production in Brazil continues to break records, mainly through first-generation (1G) ethanol from sugarcane. However, a major challenge is the large volume of vinasse produced — about 16 m3 per ton of anhydrous ethanol (Hadavifar et al., 2010). Vinasse has high biochemical oxygen demand (BOD) and chemical oxygen demand (COD), low pH, and high organic load (Chitolina and Harder, 2020). Its use in fertigation requires careful monitoring to avoid soil saturation and salinization (Mohanavelu et al., 2021; Wang et al., 2023).

The sixth United Nations Sustainable Development Goal (SDG) focuses on the conservation and responsible use of water resources, encouraging circular economy actions: reduce, reuse, recycle, and recover. In this context, wastewater treatment, especially through advanced oxidation processes (AOPs), is essential. AOPs are cost-effective and efficient in removing toxic and recalcitrant pollutants (Garrido-Cardenas et al., 2020; Ma et al., 2021). They use secondary oxidants like hydroxyl radicals (•OH) and outperform conventional treatments with high oxidation efficiency and no secondary pollution (Fernandes et al., 2019; Souza et al., 2015). Combined AOPs can enhance performance and address the limitations of traditional methods (Dewil et al., 2017).

Within the AOPs, the Fenton reaction stands out. It is used for a wide variety of effluents (Dong, Xing and Zhang, 2020). Its advantages include operating under ambient temperature and pressure conditions and the absence of hazardous reagents or sophisticated equipment, making it industrially desirable (Domingues et al., 2018).

The objective of the present study was to quantify the optimal dosage of the iron (II) ion/hydrogen peroxide (Fe2+/H2O2) reagent pair in the Fenton reaction for vinasse treatment and to elucidate the effect of the Fenton reaction after treatment in agricultural soil columns.

MATERIAL AND METHODS

Vinasse Characterization

The vinasse used in the Fenton reaction optimization experiments was obtained from the sugarcane ethanol mill Denusa (Destilaria Nova União S.A.), located in the municipality of Jandaia, Goiás state, in the Midwest region of Brazil. The effluent was generated from 1G ethanol distillation process, derived from the fermentation of sugarcane juice.

The sample was collected directly at the outlet of the industrial process after the distillation step, stored in previously cleaned polyethylene containers, and kept under refrigeration at 4°C until the experiments were carried out to minimize physicochemical and microbiological changes.

Before treatment, raw vinasse was homogenized and had its main physicochemical parameters identified. These initial analyses provided reference conditions for in natura vinasse and supported the definition of reagent dosages applied during the Fenton reaction optimization stage.

Fenton Reaction Tests for Vinasse Degradation

The experiments were performed in a factorial arrangement (Table 1), using five concentrations of [Fe2+] and five of [H2O2], with three replicates. The concentrations were expressed as percentages: 0, 25, 50, 75, and 100%, totaling 75 samples.

Table 1
Factorial experimental design (2x5) of the Fenton reaction.

To determine the dosages of peroxide and iron to be used, the equations were applied as described by Adário (2014). Iron (II) sulfate heptahydrate (FeSO4 7H2O), analytical grade (minimum purity 99%) (Dinâmica LTDA), was used as a catalyst. Hydrogen peroxide concentration was 30% (100 volumes), analytical grade (Êxodo Científica).

For 1 L of sample, after pH adjustment to 3.5 with 1M H2SO4, the catalyst and hydrogen peroxide were added and mixed at 100 rpm for one hour in a jar test. Parameters such as pH, turbidity, total dissolved solids, temperature, COD, BOD, nutrients, metals, and organic and dry matter were analyzed (APHA, 2012; EMBRAPA, 2017).

The response variable chosen for optimization and statistical modeling was the percentage removal of COD (APHA, 2012).

Statistical Modeling for Reagent Dosage Optimization in the Fenton Reaction

Modeling was performed using the R software (R Development Core Team, 2008). The data were submitted to analysis of variance (ANOVA) by the F-test at the level of 5% probability, and, in case of significance (Pagotto and Rodrigues, 2020), regression analysis was performed for Fe2+ and H2O2 dosages.

Leaching studies in soil columns

Leaching experiments in soil columns were conducted under protected laboratory conditions at the Hydraulic and Irrigation Laboratory of Instituto Federal Goiano, Rio Verde Campus. PVC columns with dimensions of 0.25 m in height and 0.07 m in internal diameter were used and filled with approximately 805.28 cm3 of soil.

The soil experiments were conducted at Instituto Federal Goiano, Rio Verde Campus, using a 3 × 2 factorial experimental design with three replicates. The evaluated factors consisted of three types of percolating liquids (distilled water, in natura vinasse, and vinasse treated by the Fenton reaction) and two soil types (sandy and clay), totaling 18 experimental units.

The soils were collected from areas near the municipality of Rio Verde, Goiás state, Brazil. The clay soil was classified as a dystrophic Red Latosol with medium to clayey texture (dfRL), while the sandy soil corresponded to an Orthic Quartzarenic Neosol (oQN). The clay soil presented a bulk density of 1.2 g cm−3 and the sandy soil 1.6 g cm−3. Both soils were used without compaction, and the soil volume was adjusted to the container capacity.

Each column was connected at the top to a reservoir containing the respective percolating liquid, with flow regulated by gravity-driven flow controllers similar to those used in hospital infusion systems. The liquid percolated vertically through the soil profile and was collected in containers positioned at the base of the columns.

During the experiment, soil moisture, electrical conductivity, and temperature were monitored for 24 hours for all treatments. After completion of the leaching test, soil samples were collected, air-dried, gently crushed, and sieved through a 2-mm mesh. Subsequently, phosphorus, potassium, and sulfur contents in the soil were determined according to the methodologies described in the EMBRAPA Soil Analysis Methods Manual (EMBRAPA, 2017).

Statistical Analysis

Data obtained from the soil column experiment were subjected to ANOVA according to the factorial design employed. When significant effects were detected, means were compared using Tukey's test at a 5% probability level (p < 0.05), employing the SISVAR® software (Ferreira, 2011).

RESULTS AND DISCUSSION

The results are presented in two stages. First, the optimization of the Fenton reaction applied to sugarcane vinasse is discussed, focusing on organic matter removal and process efficiency. Subsequently, the effects of applying treated and untreated vinasse on soil properties are evaluated through soil column leaching experiments.

Statistical Modeling for Reagent Dosage Optimization in the Fenton Reaction

ANOVA showed that the iron and hydrogen peroxide factors, as well as their interaction, were significant at the 1% probability level by the F-test. The coefficient of variation (CV) was 7.97%, indicating optimal experimental precision (Pimentel-Gomes, 2009). The significant interaction confirms that both iron and hydrogen peroxide are essential for hydroxyl radical generation in different amounts, depending on the concentration of the reaction medium (Silva et al., 2024; Zhao et al., 2024). The combined effect of these reagents enhances process efficiency (Módenes et al., 2012; Ribeiro et al., 2020). The interaction was therefore evaluated separately by testing concentration levels of 0, 25, 50, 75, and 100%. The breakdown of iron within hydrogen peroxide levels is illustrated in Figure 1.

Figure 1
Deployments of iron within each peroxide level for chemical oxygen demand removal.

When iron concentrations were evaluated within each hydrogen peroxide level (Figure 1), it was observed that, in the absence of H2O2, the average COD removal (55.22%) was mainly associated with coagulation promoted by iron ions. At intermediate H2O2 levels (25 and 50%), COD removal ranged approximately from 52.87 to 70.23% and from 50.14 to 77.49%, respectively, and was described by quadratic models indicating the existence of optimal iron levels. At higher peroxide concentrations (75 and 100%), a marked increase in COD removal was observed, with values exceeding 80% under higher iron dosages, evidencing the synergistic effect between the catalyst and the oxidant.

Increasing H2O2 concentration improves COD removal (Morshed et al., 2020). However, excessive amounts may lead to the formation of hydroperoxyl radicals with lower oxidizing power and promote self-decomposition, reducing process efficiency (Bezsenyi et al., 2021; Mohajeri et al., 2010). At low levels, peroxide is rapidly consumed (Trigueros et al., 2019), whereas at very high concentrations it may react with hydroxyl radicals, forming less effective radical–peroxide species (Santos-Juanes et al., 2011).

The breakdown of hydrogen peroxide at each iron level is shown in Figure 2. At the Fe2+ 0% level, the interaction was not significant at 5%, indicating that hydrogen peroxide remained unchanged due to the absence of an oxidative reaction in the absence of iron ions (Ameta and Ameta, 2018; Pignatello, Oliveros and MacKay, 2006). At intermediate Fe2+ levels, particularly at 25 and 75%, COD removal varied according to hydrogen peroxide concentration, whereas at the Fe2+ 100% level, the highest overall removal efficiencies were achieved.

Figure 2
Breakdown of hydrogen peroxide at each iron level for chemical oxygen demand removal.

These results highlight the dual role of iron, which acts both as a catalyst and as a potential scavenger of excess radicals, reinforcing the need to optimize the Fe2+/H2O2 ratio (Amaral et al., 2017; Gogate and Pandit, 2004). Iron ions intensify the Fenton reaction by catalyzing the reduction of H2O2 to hydroxyl radicals and promoting the oxidation of organic matter (Chen et al., 2023; Mahtab, Islam and Farooqi, 2021). Higher iron concentrations improve COD removal. However, excess iron leads to increased total dissolved solids (Gogate and Pandit, 2004), making dosage optimization essential.

In addition, iron may act as a hydroxyl radical scavenger, leading to the formation of hydroperoxyl radicals, which are less reactive and compete with hydroxyl radicals (Amaral et al., 2017). Observing the molar ratio between iron and peroxide is therefore fundamental, as both may compete within the reaction medium (Khodadadi et al., 2020).

Recent advances in Fenton-like reactions highlight the critical role of optimizing reagent ratios to balance hydroxyl radical production and scavenging phenomena. Excessive dosages of Fe2+ or H2O2 can promote radical scavenging and side reactions, reducing overall oxidation efficiency and necessitating careful operational control in large-scale applications (Xiao et al., 2024).

Based on statistical modeling and operational efficiency criteria, the Fe2+:H2O2 ratio of 50%:75% was defined as the optimal condition for vinasse degradation, supporting the subsequent stages of the study.

Efficiency of the reaction in degrading vinasse after one hour

The experiment identified as optimal in terms of concentration optimization was [Fe2+]:[H2O2]= 50%:75%, based on the lowest cost value predicted by the Scott-Knott analysis and the results in Table 2.

Table 2
Study of vinasse degradation by Fenton - 1 hour.

The COD removal results align with literature values, ranging from 5 to 47% (Yang et al., 2008). At one hour, despite satisfactory COD removal (48.59%), peroxide degradation limits radical generation (Mousavi et al., 2011; Oturan and Aaron, 2014). The COD removal achieved in this study (78.14% after 60 min) is consistent with the performance reported for Fenton-based treatments applied to sugarcane vinasse, which typically reach substantial organic matter reduction under optimized Fe/H2O2 ratios and acidic pH. For example, Guerreiro et al. (2016) reported COD removals up to 69.2% when coagulation/flocculation was combined with Fenton oxidation, highlighting the relevance of iron availability and oxidant dosing strategy to maximize treatment efficiency while controlling reagent consumption.

After 60 minutes of reaction, phosphorus removal reached 75.6%. This is essential to prevent eutrophication and anoxic conditions in aquatic systems (Naspolini et al., 2017; Ngatia and Taylor, 2018). Nitrogen removal reached 35%. This confirms the efficiency of the Fenton process in reducing nitrogen content (Kochany and Lipczynska-Kochany, 2009). Ammoniacal nitrogen was completely removed at all treatment times, with no detection. Its elimination is crucial, as oxidized nitrogen contaminates water bodies and indicates organic matter stabilization (Alaburda and Nishihara, 1998).

Turbidity was completely removed at all intervals, reaching zero at 1 hour. This is mainly due to the elimination of melanoidins, compounds responsible for vinasse coloration (Cabrera-Díaz et al., 2016). The rise in total dissolved solids is due to sludge formation from oxidation, iron coagulation during neutralization, ferric precipitation, and residual organic substances (Justino et al., 2019).

Kastanek et al. (2023) highlight that the Fenton reaction rapidly generates hydroxyl radicals during the early stages of the process, resulting in most of the oxidation occurring within the initial reaction period. Extending the reaction time beyond this phase often leads to diminishing gains in removal efficiency, as radical availability decreases due to hydrogen peroxide decomposition and increased competition from radical scavenging reactions.

Leaching study in soil elution columns

Effects of humidity, electrical conductivity, and temperature

The leaching test monitored humidity, electrical conductivity, and temperature in soil columns over 24 hours using in natura vinasse, treated vinasse (Results Table 2), and distilled water (Figure 3). In this study, the term ‘treated vinasse’ refers to vinasse subjected to the Fenton oxidation process under optimized conditions. The expression ‘vinasse treated with Fenton’ is used to explicitly indicate that the treatment consisted of an advanced oxidation process based on the Fenton reaction, involving the catalytic decomposition of hydrogen peroxide by ferrous ions.

Figure 3
Humidity behavior (A), electrical conductivity (B), and temperature (C) of different types of soils subjected to different sources of leachate in elution columns.

Treated vinasse showed superior moisture retention in clay soil, with a 67.4% increase in the first hour and 123.9% from 15 to 24 hours, totaling 182.4%. This highlighted the higher water retention capacity of clay soil compared to sandy soil, which is more permeable (Li et al., 2021). In sandy soil, treated vinasse increased moisture by 44.6% over 24 hours. Fenton-treated vinasse performed better than in natura vinasse, especially in clay soil, and demonstrated gradual and sustained moisture release.

The application of in natura vinasse increased soil salinity and electrical conductivity (Figure 3B) due to its high ionic content (Madejón et al., 2001; Ortegón et al., 2016). In sandy soil, treated vinasse resulted in more stable electrical conductivity values throughout the experiment, reflecting the lower water retention capacity and the rapid percolation of the solution through the soil profile. In the clay soil, electrical conductivity showed a significant increase after 13 hours, which was attributed to greater water retention and the progressive release of ions into the soil solution as the percolation front advanced through the profile. This behavior was directly related to the higher water retention capacity and greater specific surface area of clay soils, which favored the accumulation and mobilization of ionic species over time (Machado et al., 2006).

The lower increase in electrical conductivity observed with treated vinasse compared to in natura vinasse indicated a reduced risk of soil salinization. This behavior demonstrated that the Fenton treatment not only improved effluent quality but also mitigated potential environmental impacts associated with vinasse application, particularly in soils with higher water retention capacity, as highlighted in assessments emphasizing the need for vinasse treatment to minimize salinity-related risks (Reis and Hu, 2017).

In clay soil, in natura vinasse also increased electrical conductivity, but to a lesser extent than treated vinasse when relative values were considered. After 24 hours, treated vinasse increased electrical conductivity by 14.9% in sandy soil and 2,154% in clay soil. However, this high relative increase is associated with very low initial conductivity values and does not indicate higher absolute salinity compared to in natura vinasse. The increase was primarily linked to the addition of sodium hydroxide during pH correction, which raised Na+ concentrations and, consequently, electrical conductivity (Mundim et al., 2019). Despite this effect, absolute conductivity values remained lower than those observed for in natura vinasse, reinforcing the lower salinization risk associated with treated vinasse. Distilled water, with no dissolved ions, maintained electrical conductivity at zero throughout the experiment.

In natura vinasse caused a sharp increase in conductivity: 12,335% in sandy soil and 1,933% in clay soil. In contrast, treated vinasse showed a lower conductivity rise in both soils. This indicates its reduced potential for a negative impact on soil quality.

As it was a controlled environment, the temperature remained stable during the 24-hour period of the test (Figure 3C), being close to 25°C (average). Observing this parameter is important because the hydraulic conductivity of the soil changes by about 3% for every 1°C variation, and it influences the drying of the column (Cunha et al., 2007).

Statistical evaluation of potassium, phosphorus, and sulfur in the soil

ANOVA results show that leachates significantly influenced potassium, phosphorus, and sulfur levels at 1% by the F-test. Potassium and sulfur were significant across all soils, but phosphorus was not. The interaction between leachates and soils was significant at 1% for potassium and sulfur, and at 5% for phosphorus. Table 3 shows the unfolding of the interactions between the different types of soils and the different types of leachates.

Table 3
Unfolding of the interaction between different types of soils subjected to different sources of leachates for phosphorus, potassium, and sulfur from an elution column.

Phosphorus levels in leachates were similar when using treated vinasse and distilled water. Treated vinasse reduced phosphorus leaching by 69.5% in clay soil and 55.19% in sandy soil compared to in natura vinasse, which increased phosphorus in clay soil by 13.8%. Despite higher retention, clay soils offer less available phosphorus (Silva and Griebeler, 2007; Souza et al., 2006), and treated vinasse helps minimize absorption issues from excess organic matter (Vinha et al., 2021). Potassium levels rose more in clay soil due to its high cation adsorption capacity (Moldoveanu; Papangelakis et al., 2021). Increases were 111.5% with treated vinasse, 200% with in natura vinasse, and 146.7% with water. Soils with high cation exchange capacity (CEC), such as those found in the Cerrado, are more susceptible to K+ leaching (Werle et al., 2008), since CEC is a fundamental soil property that influences nutrient retention and ionic mobility in the soil matrix.

Soil porosity directly affects solute movement, interaction, percolation speed, and organic matter content (Moldoveanu; Papangelakis et al., 2021). Clay soils show stronger potassium retention due to higher adsorption capacity (Ćwielag-Piasecka et al., 2021). This retention is more pronounced in upper layers compared to sandy soils (Niu et al., 2022).

The sulfur content in the soil and distilled water was statistically equal. For treated vinasse, clay soil had a rate of adsorption 6.7% higher compared to sandy soil. In natura vinasse had the same higher absorption behavior as in clay soil, with a total of 48.4%. Treated vinasse had an increase of 156% compared to in natura vinasse in sandy soil, and 112.2% in clay soil.

The rise in sulfur content in treated vinasse is due to FeSO4·7H2O used as a catalyst, which releases sulfates (SO42-) into the effluent and soil. Also, vinasse naturally contains high sulfur levels from industrial processes, like sulfuric acid use in fermentation (Oliveira et al., 2020), further contributing to soil accumulation.

Sulfur is essential for plant development and often deficient in Cerrado soils (Amaral et al., 2017; Oliveira et al., 2020). Along with potassium and phosphorus, it boosts rooting, tillering, and sugarcane productivity (Pereira et al., 2020; Santos et al., 2011). Proper soil management is crucial to ensure their availability.

For the application of treated vinasse, CEC was 3.38 cmolc dm−3 in sandy soil and 12.30 cmolc dm−3 in clay soil. For in natura vinasse, it was 9.08 cmolc dm−3 in sandy soil and 23.29 cmolc dm−3 in clay soil. For distilled water, it was 3.16 cmolc dm−3 in sandy soil and 13.85 cmolc dm−3 in clay soil. The increase in CEC in soils under the application of in natura vinasse is observed since there is a greater load of nutrients (Leão et al., 2022), influencing the total sum of loads present in the colloidal complex.

Most Brazilian soils are naturally acidic and require correction (Pereira et al., 2020). In natura vinasse kept pH low (5.20 sandy, 5.55 clay), while treated vinasse raised it to near neutrality (7.20 sandy, 7.25 clay), favoring nutrient absorption. The ideal pH range for uptake of essential nutrients is 6.0 to 7.0 (Malavolta, 1979; Moreira; Bernardi, 2008).

Treated vinasse preserved nutrient supply while correcting soil pH without liming, lowering costs. It enabled better control of dosage, avoiding soil salinization, leaching, and groundwater contamination (Daba and Qureshi, 2021; Francisco et al., 2015). It also reduced excess organic matter, preventing ionic imbalance and the formation of sacrificial areas.

Overall, nutrient behavior in the soil columns was strongly influenced by soil texture and cation exchange capacity, which jointly controlled nutrient retention and mobility. Clay soils exhibited greater nutrient retention due to their higher specific surface area and abundance of exchange sites, whereas sandy soils showed higher nutrient mobility and a greater susceptibility to downward transport. This contrasting behavior is consistent with reports on vinasse application, in which soil texture governs nutrient retention, leaching potential, and associated environmental risks in the unsaturated zone (Ortegón et al., 2016). In this context, a comparative study on soil textures demonstrated that potassium losses are strongly controlled by soil physicochemical attributes and water fluxes, with coarser-textured soils being more vulnerable to leaching (Mendes et al., 2016). Therefore, the reduced nutrient accumulation and leaching observed with treated vinasse in the present study indicate a more balanced nutrient supply and improved environmental safety compared to in natura vinasse.

Long-term evaluations also indicate that vinasse application can markedly increase nutrient contents and alter soil properties in both clay and sandy systems, although the magnitude of change and environmental risk differs by texture (Cardoso; Coelho; Fernandes, 2021). Importantly, field-scale monitoring has demonstrated that high ionic loads from vinasse may translate into increases in major ions in the vadose zone and groundwater, reinforcing the need for treatments that reduce salinity and nutrient overload before soil application (Ortegón et al., 2016).

Recent evidence further highlights that vinasse-derived leachates can mobilize dissolved constituents under percolation, and mitigation strategies are particularly relevant in permeable soils (Amin, 2024). Therefore, the lower ionic impact observed with treated vinasse in the present study supports its use as a safer alternative to minimize nutrient losses and reduce the potential for salinization and subsurface contamination, especially in sandy soils.

CONCLUSION

The results demonstrated that the Fenton process was highly effective, achieving 78.14% chemical oxygen demand removal and complete turbidity reduction, in addition to reducing macro and micronutrient concentrations to levels compatible with safe agricultural use.

The application of treated vinasse increased soil moisture without causing surface accumulation or ponding, in contrast to in natura vinasse, and contributed to soil pH correction without the need for chemical liming. Soil column experiments indicated a lower risk of salinization, nutrient leaching, and groundwater contamination when vinasse was previously treated.

Therefore, fertigation with vinasse treated by the Fenton process represents a technically feasible and environmentally safe alternative for the reuse of this effluent, contributing to sustainable water management and the gradual supply of nutrients required for sugarcane cultivation, particularly during periods of water deficit.

  • Funding:
    CAPES (grant no. 88887710669/2022-00), FAPEG (grant no. 202310267000825) and CNPq (grant no. 302542/2023-0).

DATA AVAILABILITY STATEMENT

The datasets generated and/or analyzed during the current study are available from the corresponding author upon reasonable request.

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Edited by

Publication Dates

  • Publication in this collection
    29 June 2026
  • Date of issue
    2026

History

  • Received
    14 Apr 2025
  • Accepted
    07 Mar 2026
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