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Husks of rice (RH), coffee (CH), and cholupa (CLH) were used to produce natural adsorbents. The natural adsorbents were used to remove pharmaceuticals such as diclofenac, ciprofloxacin, and acetaminophen in a mixture of distilled water. However, CH stood out for its efficiency in removing ciprofloxacin (74%) due to the higher concentration of acidic groups, as indicated by the Boehm method. In addition, CH removed 86% of ciprofloxacin individually. Therefore, CH was selected and used to remove other fluoroquinolones, such as levofloxacin and Norfloxacin. Although electrostatic interactions favored removals, better removal was observed for ciprofloxacin due to its smaller molecular volume. Then, ciprofloxacin was selected, and the effect of pH, matrix, and adsorbent doses were evaluated. In this way, using a pH of 6.2 in urine with a dose of 1.5 g L-1, it is possible to adsorb CIP concentrations in the range (0.0050-0.42 mmol L-1). Subsequently, the high R2 values and low percentages of APE and Δq indicated better fits for pseudo-second-order kinetics, suggesting a two-stage adsorption. At the same time, the Langmuir isotherm recommends a monolayer adsorption with a Qm of 25.2 mg g-1. In addition, a cost of 0.373 USD/g CIP was estimated for the process, where the material can be reused up to 4 times with a CIP removal in the urine of 51%. Consequently, thermodynamics analysis showed an exothermic and spontaneous process with high disorder. Furthermore, changes in FTIR analysis after adsorption suggest that CH in removing CIP in urine involves electrostatic attractions, hydrogen bonds and π-π interactions. In addition, the life cycle analysis presents, for the 11 categories evaluated, a lower environmental impact of the CIP removal in urine with CH than for the preparation of adsorbent, confirming that the adsorption process is more environmentally friendly than materials synthesis or other alternatives of treatments. Furthermore, future directions of the study based on real applications were proposed.

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In this study, UiO-67 (Zr)/g-C3N4 composites (U67N) were synthesized at wt.% ratios of 05:95, 15:85, and 30:70 using the solvothermal method at 80 °C for 24 h followed by calcination at 350 °C. The composites were characterized using UV-Vis diffuse reflectance spectroscopy, Fourier-transform infrared spectroscopy, photoluminescence spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscopy-energy-dispersive X-ray spectroscopy, transmission electron microscopy, and nitrogen physisorption analysis. In addition, thermal stability analysis of UiO-67 was conducted using thermogravimetric analysis. The photocatalytic performance of the composites was assessed during the degradation and mineralization of a mixture of methylparaben (MeP) and propylparaben (PrP) under simulated sunlight. The adsorption process of U67N 15:85 was characterized through kinetic studies and adsorption capacity experiments, which were modeled using pseudo-first-order and pseudo-second-order kinetics and Langmuir and Freundlich isotherms, respectively. The influence of pH levels 3, 5, and 7 on the photocatalytic degradation of the mixture was investigated, revealing enhanced degradation and mineralization at pH 3. The U67N composite exhibited dual capability in removing contaminants through adsorption and photocatalytic processes. Among the prepared composites, U67N 15:85 demonstrated the highest photocatalytic activity, achieving removal efficiencies of 96.8% for MeP, 92.5% for PrP, and 45.7% for total organic carbon in 300 kJ/m2 accumulated energy (3 h of reaction time). The detoxification of the effluent was confirmed through acute toxicity evaluation using the Vibrio fischeri method. The oxidation mechanism of the heterojunction formed between UiO-67 (Zr) and g-C3N4 was proposed based on PL analysis, photoelectrochemistry studies (including photocurrent response, Nyquist, and Mott-Schottky analyses), and scavenger assays.

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Reducing high concentrations of pollutants such as heavy metals, pesticides, drugs, and dyes from water is an emerging necessity. We evaluated the use of Luffa cylindrica (Lc) as a natural non-conventional adsorbent to remove azo dye mixture (ADM) from water. The capacity of Lc at three different doses (2.5, 5.0, and 10.0 g/L) was evaluated using three concentrations of azo dyes (0.125, 0.250, and 0.500 g/L). The removal percent (R%), maximum adsorption capacity (Qm), isotherm and kinetics adsorption models, and pH influence were evaluated, and Fourier-transform infrared spectroscopy and scanning electron microscopy were performed. The maximum R% was 70.8% for 10.0 g L-1Lc and 0.125 g L-1 ADM. The Qm of Lc was 161.29 mg g-1. Adsorption by Lc obeys a Langmuir isotherm and occurs through the pseudo-second-order kinetic model. Statistical analysis showed that the adsorbent dose, the azo dye concentration, and contact time significantly influenced R% and the adsorption capacity. These findings indicate that Lc could be used as a natural non-conventional adsorbent to reduce ADM in water, and it has a potential application in the pretreatment of wastewaters.

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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 study, we analyzed the impact of hydroxyl and epoxy groups on the properties of graphene oxide (GO) for the adsorption of methylene blue (MB) dye from water, addressing the urgent need for effective water purification methods due to industrial pollution. Employing a dual approach, we integrated experimental techniques with theoretical modeling via density functional theory (DFT) to examine the atomic structure of GO and its adsorption capabilities. The methodology encompasses a series of experiments to evaluate the performance of GO in MB dye adsorption under different conditions, including differences in pH, dye concentration, reaction temperature, and contact time, providing a comprehensive view of its effectiveness. Theoretical DFT calculations provide insights into how hydroxyl and epoxy modifications alter the electronic properties of GO, improving adsorption efficiency. The results demonstrate a significant improvement in the dye adsorption capacity of GO, attributed to the interaction between the functional groups and MB molecules. This study not only confirms the potential of GO as a superior adsorbent for water treatment, but also contributes to the optimization of GO-based materials for environmental remediation, highlighting the synergy between experimental observations and theoretical predictions in advances in materials science to improve sustainability.

RESUMO

Driven by climate change and human activity, Sargassum blooming rates have intensified, producing copious amount of the invasive, pelagic seaweed across the Caribbean and Latin America. Battery recycling and lead-smelter wastes have heavily polluted the environment and resulted in acute lead poisoning in children through widespread heavy metal contamination particular in East Trinidad. Our study details a comprehensive investigation into the use of Sargassum (S. natans), as a potential resource-circular feedstock for the synthesis of calcium alginate beads utilized in heavy metal adsorption, both in batch and column experiments. Here, ionic cross-linking of extracted sodium alginate with calcium chloride was utilized to create functional ion-exchange beads. Given the low quality of alginates extracted from Sargassum which produce poor morphological beads, composite beads in conjunction with graphene oxide and acrylamide were used to improve fabrication. Stand-alone calcium alginate beads exhibited superior Pb2+ adsorption, with a capacity of 213 mg g-1 at 20 °C and pH 3.5, surpassing composite and commercial resins. Additives like acrylamide and graphene oxide in composite alginate resins led to a 21-40% decrease in Pb2+ adsorption due to reduced active sites. Column operations confirmed Alginate systems' practicality, with 20-24% longer operating times, 15 times lower adsorbent mass on scale-up and 206% smaller column diameters compared to commercial counterparts. Ultimately, this study advocates for Sargassum-based Alginate ion-exchange beads as a bio-based alternative in Trinidad and developing nations for dealing with heavy metal ion waste, offering superior heavy metal adsorption performance and supporting resource circularity.

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This study investigated the single and multicomponent adsorption of three emerging pollutants, the basic dyes Rhodamine 6G (R6G), Auramine-O (AO), and Brilliant Green (BG) by using hydroxyapatite synthesized from Pirarucu scales as adsorbent (HAP). The adsorption process was studied using seven different systems: AO-single, R6G-single, BG-single, R6G + AO, BG + AO, BG + R6G, and R6G + AO + BG. For kinetics, the initial concentration of each adsorbate per system was 50 mg/L, the results showed that the singular adsorption of these dyes was best-represented by the pseudo-second-order model (qAO = 62.54 mg/g, qR6G = 7.91 mg/g, qBG = 62.40 mg/g), however, the multicomponent adsorption was well-fitted by a pseudo-first-order model (ternary system: qAO = 56.21 mg/g, qR6G = 14.95 mg/g, qBG = 60.62 mg/g). For equilibrium, the initial concentration of each adsorbate per system was 10-300 mg/L, and the single adsorption systems were best represented by the Langmuir model. Nonetheless, the results displayed in the multicomponent mixture showed the presence of inflection points of AO and R6G whenever BG was present in solution with C0 > 150 mg/L, thus indicating that BG has greater affinity with HAP. The presence of inflection points in the curves represented a limitation for applying traditional equilibrium models, thus, an artificial neural network (ANN) was applied to non-linear curve fit this process and satisfactorily predicted the kinetics and equilibrium data. Finally, the analysis of thermodynamics for the ternary mixture revealed that the adsorption process is spontaneous (ΔG < 0), endothermic (ΔH > 0), and increases to a disorganized state as the temperature rises (ΔS > 0).

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This study explores cutting-edge and sustainable green methodologies and technologies for the synthesis of functional nanomaterials, with a specific focus on the removal of water contaminants and the application of kinetic adsorption models. Our research adopts a conscientious approach to environmental stewardship by synergistically employing eco-friendly silver nanoparticles, synthesized using Justicia spicigera extract as a biogenic reducing agent, in conjunction with Mexican zeolite to enhance contaminant remediation, particularly targeting Cu2+ ions. Structural analysis, utilizing X-ray diffraction (XRD) and high-resolution scanning and transmission electron microscopy (TEM and SEM), yields crucial insights into nanocomposite structure and morphology. Rigorous linear and non-linear kinetic models, encompassing pseudo-first order, pseudo-second order, Freundlich, and Langmuir, are employed to elucidate the kinetics and equilibrium behaviors of adsorption. The results underscore the remarkable efficiency of the Zeolite-Ag composite in Cu2+ ion removal, surpassing traditional materials and achieving an impressive adsorption rate of 98% for Cu. Furthermore, the Zeolite-Ag composite exhibits maximum adsorption times of 480 min. In the computational analysis, an initial mechanism for Cu2+ adsorption on zeolites is identified. The process involves rapid adsorption onto the surface of the Zeolite-Ag NP composite, followed by a gradual diffusion of ions into the cavities within the zeolite structure. Upon reaching equilibrium, a substantial reduction in copper ion concentration in the solution signifies successful removal. This research represents a noteworthy stride in sustainable contaminant removal, aligning with eco-friendly practices and supporting the potential integration of this technology into environmental applications. Consequently, it presents a promising solution for eco-conscious contaminant remediation, emphasizing the utilization of green methodologies and sustainable technologies in the development of functional nanomaterials.

RESUMO

The potential of pyrolyzed Mytella falcata shells as an adsorbent for removing methylene blue dye molecules from aqueous solutions was investigated. The study found that the adsorbent produced at 600 °C of pyrolysis temperature, with an adsorbent mass of 0.5 g, particle diameter of 0.297-0.149 mm, and pH 12.0, demonstrated the highest dye molecule removal efficiency of 82.41%. The material's porosity was observed through scanning electron microscopy, which is favorable for adsorption, while Fourier-transform infrared spectroscopy and X-Ray diffraction analysis analyses confirmed the presence of calcium carbonate in the crystalline phases. The pseudo-second order model was found to be the best fit for the data, suggesting that the adsorption mechanism involves two steps: external diffusion and diffusion via the solid pores. The Redlich-Peterson isotherm model better represented the equilibrium data, and the methylene blue adsorption was found to be spontaneous, favorable, and endothermic. The hydrogen peroxide with UV oxidation was found to be the most efficient method of regeneration, with a regeneration percentage of 63% achieved using 600 mmol.L-1 of oxidizing agents. The results suggest that pyrolyzed Mytella falcata shells could serve as an ecologically viable adsorbent alternative, reducing the amount of waste produced in the local environment and at the same time removing pollutants from the water. The material's adsorption capacity remained almost constant in the first adsorption-oxidation cycles, indicating its potential for repeated use.

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A magnetic hydrogel based on xylan (X), poly (acrylic acid), and maghemite (γ-Fe2O3) named HXA-Fe2O3 was synthesized, characterized, and applied as an alternative material to remove methylene blue (MB) from aqueous media by adsorption. Maghemite was synthesized by coprecipitation method and later incorporated in the hydrogel matrix synthesized by free radical polymerization. The characterization studies included FTIR, DSC, XRD, VSM, Zeta Potential, TGA, SEM, TEM, and N2 adsorption isotherms (BET). The physicochemical characterization results confirmed the intended synthesis and showed the compositional, thermal, structural, morphological, textural, and magnetic profile of the materials. The adsorption studies included experimental design, kinetic, and isotherm. A full factorial design was employed considering the factors adsorbent dosage (g L-1), pH, and ionic strength (mmol L-1 of NaCl) for adsorption capacity and removal percentage responses. As ionic strength was not significant, a Doehlert design was employed with adsorbent dosage and pH, indicating the optimal adsorption conditions. The kinetics was well described by the PSO model, while the isotherm obeyed the Sips model. Equilibrium was attained at 60 min, and the maximum experimental adsorption capacity was up to 250.26 mg g-1 at pH 8.5, adsorbent dosage of 0.2 g L-1, and 298 K. These findings show that the magnetic hydrogel produced has great potential to be applied in the adsorption of basic molecules, such as MB.