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The presence of phenazopyridine in water is an environmental problem that can cause damage to human health and the environment. However, few studies have reported the adsorption of this emerging contaminant from aqueous matrices. Furthermore, existing research explored only conventional modeling to describe the adsorption phenomenon without understanding the behavior at the molecular level. Herein, the statistical physical modeling of phenazopyridine adsorption into graphene oxide is reported. Steric, energetic, and thermodynamic interpretations were used to describe the phenomenon that controls drug adsorption. The equilibrium data were fitted by mono, double, and multi-layer models, considering factors such as the numbers of phenazopyridine molecules by adsorption sites, density of receptor sites, and half saturation concentration. Furthermore, the statistical physical approach also calculated the thermodynamic parameters (free enthalpy, internal energy, Gibbs free energy, and entropy). The maximum adsorption capacity at the equilibrium was reached at 298 K (510.94 mg g-1). The results showed the physical meaning of adsorption, indicating that the adsorption occurs in multiple layers. The temperature affected the density of receptor sites and half saturation concentration. At the same time, the adsorbed species assumes different positions on the adsorbent surface as a function of the increase in the temperature. Meanwhile, the thermodynamic functions revealed increased entropy with the temperature and the equilibrium concentration.

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Herein, graphene oxide was used as the highly efficient phenazopyridine adsorbent from aqueous medium, synthetic, and human urine. The nanoadsorbent was characterized by different instrumental techniques. The adsorption capacity (1253.17 mg g-1) was reached at pH 5.0, using an adsorbent dosage of 0.125 g L-1 at 298 K. The Sips and Langmuir described the equilibrium data well. At the same time, the pseudo-second order was more suitable for fitting the kinetic data. Thermodynamic parameters revealed the exothermic nature of adsorption with an increase in randomness at the solid-liquid interface. The magnitude of the enthalpy variation value indicates that the process involves the physisorption phenomenon. At the same time, ab initio molecular dynamics data corroborated with the thermodynamic results, indicating that adsorbent and adsorbate establish hydrogen bonds through the amine groups (adsorbate) and hydroxyl groups on the adsorbent surface (weak interactions). Electrostatic interactions are also involved. Additionally, the adsorption assays conducted in simulated medium and human urine showed the excellent performance of adsorbent material to remove the drug in real concentrations excreted by the kidneys (removal values higher than 60%).

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Naphthenic acids (NA) are organic compounds commonly found in crude oil and produced water, known for their recalcitrance and toxicity. This study introduces a new adsorbent, a polymer derived from spent coffee grounds (SCGs), through a straightforward cross-linking method for removing cyclohexane carboxylic acid as representative NA. The adsorption kinetics followed a pseudo-second-order model for the data (0.007 g min-1 mg-1), while the equilibrium data fitted the Sips model ( q m = 140.55 mg g-1). The process's thermodynamics indicated that the target NA's adsorption was spontaneous and exothermic. The localized sterical and energetic aspects were investigated through statistical physical modeling, which corroborated that the adsorption occurred indeed in monolayer, as suggested by the Sips model, but revealed the contribution of two energies per site ( n 1 ; n 2 ). The number of molecules adsorbed per site ( n ) was highly influenced by the temperature as n 1 decreased with increasing temperature and n 2 increased. These results were experimentally demonstrated within the pH range between 4 and 6, where both C6H11COO-(aq.) and C6H11COOH(aq.) species coexisted and were adsorbed by different energy sites. The polymer produced was naturally porous and amorphous, with a low surface area of 20 to 30 m2 g-1 that presented more energetically accessible sites than other adsorbents with much higher surface areas. Thus, this study shows that the relation between surface area and high adsorption efficiency depends on the compatibility between the energetic states of the receptor sites, the speciation of the adsorbate molecules, and the temperature range studied.

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Herein, we demonstrate the prospects of tackling several environmental problems by transforming a local rice husk residue into an effective adsorbent, which was then applied for the treatment of real landfill leachate (LL). The study focused on establishing (i) the effect of simple washing on morphological aspects, (ii) evaluating target adsorption capacity for total iron (Fe) and nickel (Ni), (iii) determining regeneration and reuse potential of the adsorbent and (iv) complying to the requirements of worldwide legislations for reuse of treated LL wastewater. The adsorbent was prepared by employing a simple yet effective purification process that can be performed in situ. The LL was collected post-membrane treatment, and the characterizations revealed high concentrations of Fe, Ni, and organic matter content. The simple washing affected the crystallinity, resulting in structural alterations of the adsorbents, also increasing the porosity and specific surface. The adsorption process for Ni occurred naturally at pH 6, but adjusting the pH to 3 significantly improved removal efficiency and adsorption capacity for total Fe. The kinetics were accurately described by the pseudo-second-order model, while the Langmuir model provided a better fit for the isotherms. The adsorbent was stable for 5 reuses, and the metals adsorbed were recovered through basic leaching. The removal capacities achieved underscore the remarkable effectiveness of the process, ensuring the treated LL wastewater meets rigorous global environmental legislations for safe use in irrigation. Thus, by employing the compelling methods herein optimized it is possible to refer to the of solving three environmental problems at once.

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In this work, the adsorption of nickel ions from a real effluent from a metal-mechanic industry was investigated in a fixed-bed column using biochar. Biochar was prepared from winemaking residues originating from the Beifiur® composting process. The use of wine industry residues as precursor materials for biochar production is established in biomass residue valorization using the existing logistics and the lowest possible number of manipulations and pre-treatments. The results found in the work showed that the optimal conditions for nickel adsorption in fixed-bed columns were bed height (Z) of 7 cm, initial nickel concentration (C0) of 1.5 mg L-1, and flow rate (Q) of 18 mL min-1. In this condition, the maximum adsorption capacity of the column was 0.452 mg g-1, the mass transfer zone (Zm) was 3.3 cm, the treated effluent volume (Veff) was 9.72 L, and the nickel removal (R) was 92.71%. The Yoon-Nelson and BDST dynamic models were suitable to represent the breakthrough curves of nickel adsorption. Finally, the fixed-bed column adsorption using biochar from winemaking residues proved to be a promising alternative for nickel removal from real industrial effluents.

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In this work, iron-bearing mining reject was employed as an alternative and potential low-cost catalyst to degrade phenol in water by photo-Fenton strategy. Various techniques, including SEM-EDS, BET, FTIR, and XRD, were applied to evaluate the material's properties. Process parameters such as hydrogen peroxide concentration, catalyst dosage, and pH were studied to determine the optimum reaction conditions ([catalyst] = 0.75 g L-1, [H2O2] = 7.5 mM, and pH = 3). Phenol degradation and mineralization efficiencies at 180 and 300 min were 96.5 and 78%, respectively. These satisfactory results can be associated with the iron amount present in the waste sample. Furthermore, the material showed high catalytic activity and negligible iron leaching even after the fourth reuse cycle. The degradation behavior of phenol in water was well represented by a kinetic model based on the Fermi function. The iron-bearing mining reject can be considered a potential photo-Fenton catalyst for phenol degradation in wastewater.

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A promissory technic for reducing environmental contaminants is the production of biochar from waste reuse and its application for water treatment. This study developed biochar (CWb) and NH4Cl-modified biochar (MCWb) using cassava residues as precursors. CWb and MCWb were characterized and evaluated in removing dyes (Acid Blue 9 and Food Red 17) in a binary system. The adsorbent demonstrated high adsorption capacity at all pH levels studied, showing its versatility regarding this process parameter. The equilibrium of all adsorption experiments was reached in 30 min. The adsorption process conformed to pseudo-first-order kinetics and extended Langmuir isotherm model. The thermodynamic adsorption experiments demonstrated that the adsorption process is physisorption, exhibiting exothermic and spontaneous characteristics. MCWb exhibited highly efficient and selective adsorption behavior towards the anionic dyes, indicating maximum adsorption capacity of 131 and 150 mg g-1 for Food Red 17 and Acid Blue 9, respectively. Besides, MCWb could be reused nine times, maintaining its original adsorption capacity. This study demonstrated an excellent adsorption capability of biochars in removing dyes. In addition, it indicated the recycling of wastes as a precursor of bio composts, a strategy for utilization in water treatment with binary systems. It showed the feasibility of the reuse capacity that indicated that the adsorbent may have many potential applications.

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The present research aimed to evaluate the use of grape stalk in the adsorption of lanthanum and cerium to identify the best operating conditions enabling the application of the bioadsorbent in REEs leached from phosphogypsum. The grape stalk was characterized and showed an amorphous structure with a heterogeneous and very porous surface. Also, it was possible to identify the groups corresponding to carboxylic acids, phenols, alcohols, aliphatic acids, and aromatic rings. The pH effect study showed that the adsorption process of La3+ and Ce3+ ions was favored at pH 5.0. The adsorption kinetics followed the pseudo-second-order model. In just 20 min, 80% saturation was reached, while equilibrium was reached after 120 min. The adsorption isotherms were appropriately adjusted to the Langmuir model, and the maximum adsorption capacities were obtained at 298 K, which were 35.22 mg g-1 for La3+ and 37.99 mg g-1 for Ce3+. Furthermore, the adsorption process was favorable, spontaneous, and exothermic. In the study's second phase, phosphogypsum was leached with a sulfuric acid solution. Then, the adsorption of REEs was carried out under the experimental conditions of pH after leaching and pH 5.0 (adjustment carried out with sodium hydroxide solution) at 298 K for 120 min and with adsorbent dosages of 1 and 5 g L-1. This process resulted in removal percentages above 95% for the most abundant REEs, such as neodymium, lanthanum, and cerium, at pH 5.0 and a dosage of 5 g L-1, demonstrating the effectiveness of the bioadsorbent used. These results indicate the potential of using grape residue as a promising bioadsorbent in recovering rare earth elements from phosphogypsum leachate.

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In this study, coal bottom ash from a thermoelectric plant was tested as an alternative Fenton catalyst for phenol degradation in water. The effect of operating parameters such as initial pH, catalyst dosage and H2O2 concentration were evaluated. The characterization results indicated that the material has a mesoporous structure, with active species (Fe) well distributed on its surface. Under the optimal reaction conditions (6 mM H2O2, 1 g L-1 of catalyst and pH = 3), 98.7% phenol degradation efficiency was achieved in 60 min, as well as 71.6% TOC removal after 150 min. Hydroxyl radical was identified as the main oxidizing agent involved on the cleavage of the phenol molecule. After four consecutive reuse cycles, phenol degradation efficiency was around 80%, indicating good reusability and stability of the catalyst. Therefore, the obtained results demonstrated that the bottom ash presents remarkable activity for application in the Fenton reaction towards phenol degradation.

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Grain cultivation and its impacts on the environment have been the focus of many studies, especially due to generated solid waste and the wide use of agrochemicals aiming for greater productivity. In this context, the present study proposes a new and consistent step in constructing self-sustainability in rice farming. The proposed stage includes reusing green silica waste as an adsorbent to treat effluents contaminated by pesticides directly applied to rice cultivation. After nano silica production through the rice husks burning, followed by basic leaching and acid precipitation, a carbonaceous material remains. This material, naturally impregnated by Na2SiO3, was washed and dried, characterized, and used to remove the pesticide 2,4-dichlorophenoxyacetic acid (2,4-D). The adsorption essays were performed at 2,4-D at low concentrations (between 1 and 10 mg L-1) at different temperatures. The washed and dried porous carbon (WDPC) surface is irregular and presents slit-shaped channels. The FT-IR analysis identified the siloxane, carbonyl, carboxylate, and methylene functional groups available to interact with the pesticide molecules. The washing/drying process eliminated impurities, improving the surface area from 539.67 to 619.67 cm2 g-1 and pore volume from 0.29 to 0.44 cm3 g-1. Concerning the adsorption of 2,4-D on WDPC, the best pH was 6.0, where around 75% of the pesticide was removed from the water. The equilibrium isotherms presented an S-shaped form indicating a multilayer and cooperative adsorption, with maximum adsorption capacities of 7.504 and 7.736 mg g-1. The estimated ∆Gads, ΔHads, and ΔSads values suggested that pesticide adsorption was spontaneous, exothermic, and favorable. Finally, WDPC demonstrated a good potential to uptake 2,4-D from water, contributing to self-sustainability in rice farming.

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Graphene-based materials have increasingly attracted attention in recent years. It is a material is recognized worldwide due to its numerous applications in several sectors. However, graphene production involves several challenges: scalability, high costs, and high-quality production. This study synthesized graphene-like porous carbon nanosheets (GPCNs) through a thermochemical process under a nitrogen atmosphere using grape bagasse as a precursor. Three temperatures (700, 800, and 900 ºC) of the pyrolysis process were studied. Chemical graphitization and activation were used to form high-specific surface area materials: FeCl3.6H2O(aq) and ZnCl2(s) in a simultaneous activation-graphitization (SAG) method. The materials obtained (GPCN700, GPCN800, and GPCN900) were compared to previously produced chars (C700, C800, and C900). A high specific surface area and total pore volume were obtained for GPCN materials, and GPCN900 presented the highest values: 1062.7 m2g-1 and 0.635 cm3 g-1, respectively. The GPCN and char materials were classified as mesoporous and applied as adsorbents for CO2(g). The GPCN800 presented the best CO2(g) adsorbent, with a CO2(g) adsorption capacity of 168.71 mg g-1.

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This study was intended to valorize a floated sludge of a poultry slaughterhouse using it as a precursor to producing char and activated carbon, which were tested as adsorbents in removing ketoprofen and diclofenac sodium from the water. The addition of zinc chloride or calcium hydroxide was determinant for forming a porous carbonaceous structure with a high surface area in AC-FSP (656.54 m2 g-1), differently from that exhibited by the CHAR-FSP (8.11 m2 g-1). Kinetic and equilibrium studies indicated that the pseudo-second-order and the Sips models were suitable. The AC- FSP maximum adsorption capacity for ketoprofen and diclofenac sodium was 124.98 mg g-1 and 138.32 mg g-1, respectively. The adsorption was a spontaneous and endothermic process. It was concluded that AC-FSP is a more efficient and promising adsorbent than CHAR-FSP for the adsorption of drugs in contaminated wastewater. In addition, AC-FSP can be reused, maintaining good adsorption levels for about 5 cycles. Therefore, this study is aligned with the 2030 Agenda for global sustainability since converting waste (valueless) into an adsorbent is also directly linked to the circular economy and neutral carbon.

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This study explores the fabrication of nanofibers using different types of gelatins, including bovine, porcine, and fish gelatins. The gelatins exhibited distinct molecular weights and apparent viscosity values, leading to different entanglement behavior and nanofiber production. The electrospinning technique produced nanofibers with diameters from 47 to 274 nm. The electrospinning process induced conformational changes, reducing the overall crystallinity of the gelatin samples. However, porcine gelatin nanofibers exhibited enhanced molecular ordering. These findings highlight the potential of different gelatin types to produce nanofibers with distinct physicochemical properties. Overall, this study sheds light on the relationship between gelatin properties, electrospinning process conditions, and the resulting nanofiber characteristics, providing insights for tailored applications in various fields.

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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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The work proposes the application of a nanocomposite formed by graphene oxide and magnetite to remove chloroquine, propranolol, and metformin from water. Tests related to adsorption kinetics, equilibrium isotherms and adsorbent reuse were studied, and optimization parameters related to the initial pH of the solution and the adsorbent dosage were defined. For all pharmaceuticals, adsorption tests indicated that removal efficiency was independent of initial pH at adsorbent dosages of 0.4 g L-1 for chloroquine, 1.2 g L-1 for propranolol, and 1.6 g L-1 for metformin. Adsorption equilibrium was reached within the first few minutes, and the pseudo-second-order model represented the experimental data well. While the equilibrium data fit the Sips isotherm model at 298 K, the predicted maximum adsorption capacities for chloroquine, propranolol, and metformin were 44.01, 16.82, and 12.23 mg g-1, respectively. The magnetic nanocomposite can be reused for three consecutive cycles of adsorption-desorption for all pharmaceuticals, being a promising alternative for the removal of different classes of pharmaceuticals in water.

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In this work, CoFe2O4/TiO2 nanostructure was prepared through a facile and effective solvothermal route for efficient use in the degradation of the Erionyl Red A-3G model pollutant under ultraviolet irradiation. Characterization analysis indicated the successful heterojunction among the precursors. The composite presented band gap value of 2.75 eV, being smaller than that of the pristine TiO2, as well as mesoporous structure. The catalytic activity of nanostructure was investigated by employing a 22 factorial experimental design with 3 central points. The optimized reaction conditions were set as pH = 2 and catalyst dosage = 1.0 g L-1 for an initial pollutant concentration of 20 mg L-1. The prepared nanohybrid presented remarkable catalytic activity, reaching color removal efficiency of 95.39% after 15 min, as well as total organic carbon (TOC) removal of 69.4% after 120 min. The kinetic studies of TOC removal followed the pseudo-first order model, with a rate constant of 0.10 min-1. Moreover, the nanostructure presented magnetic behavior, being easily separated from the aqueous medium through the use of a simple external magnetic field.

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The present work synthesized two new materials of functionalized multi-walled carbon nanotubes (MWCNT-OH and MWCNT-COOH) impregnated with magnetite (Fe3O4) using solution precipitation methodology. The resulting MWCNT-OH-Mag and MWCNT-COOH-Mag materials were characterized by scanning electron microscopy coupled with energy dispersion X-ray spectroscopy, Fourier transform infrared, X-ray diffraction, atomic force microscopy, and electrical force microscopy. The characterization results indicate that the -OH functional groups in the MWCNT interact effectively with magnetite iron favoring impregnation and indicating the regular distribution of nanoparticles on the surface of the synthesized materials. The adsorption efficiency of the MWCNT-OH-Mag and MWCNT-COOH-Mag materials was tested using the pollutants 2,4-D and Atrazine. Over batch studies carried out under different pH ranges, it was found that the optimal condition for 2,4-D adsorption was at pH 2, while for Atrazine, it was found at pH 6. The rapid adsorption kinetics of 2,4-D and Atrazine reaches equilibrium within 30 min. The pseudo-first-order model described 2,4-D adsorption well. The General-order model described better atrazine adsorption. The magnetically doped adsorbent functionalized with -OH surface groups (MWCNT-OH-Mag) demonstrated superior adsorption performance and increased Fe-doped sites. The Sips model described the adsorption isotherms accurately. MWCNT-OH-Mag presented the greatest adsorption capacity at 51.4 and 47.7 mg g-1 for 2,4-D and Atrazine, respectively. Besides, electrostatic forces and complexation rule the molecular interactions between metals and pesticides. The leaching and regeneration tests of the synthesized materials indicate high stability in an aqueous solution. Furthermore, experiments with wastewater samples contaminated with the model pollutants indicate that the novel adsorbents are highly promising for enhancing water purification by adsorptive separation.

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This work focused on developing an active bilayer film based on natural extract. Thus, the jaboticaba peel extract (JPE) was produced and characterized and showed promising application as a natural additive in biopolymeric materials. The zein fiber and bilayer films were produced using a chitosan film (casting) and zein fiber (electrospinning), with and without JPE. All samples were evaluated according to thickness, solubility in water, water vapor permeability, and main diameter, and for these, zein fiber, chitosan/zein fiber, and chitosan/zein fiber + 3% JPE showed values of 0.19, 0.51, and 0.50 mm, 36.50, 12.96, and 27.38%, 4.48 × 10-9, 1.6 × 10-10, and 1.58 × 10-10 (g m-1 Pa-1 s-1), and 6.094, 4.685, and 3.620 µm, respectively. These results showed that the addition of a second layer improved the barrier properties of the material when compared to the monolayer zein fiber. The thermal stability analysis proved that the addition of JPE also improved this parameter and the interactions between the components of the zein fiber and bilayer films; additionally, the effective presence of JPE was shown through FTIR spectra. In the end, the active potential of the material was confirmed by antimicrobial analysis since the bilayer film with JPE showed inhibition halos against E. coli and S. aureus.