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In this study, municipal solid waste bottom ash (MSW-BA) and fly ash (MSW-FA) were used as a source of aluminosilicate to prepare geopolymer (GEO) adsorbents (GEO-MSWBA and GEO-MSWFA) for the removal of methylene blue (MB) from water. The effects of temperature, pH, and initial concentration on the MB adsorption onto GEO-MSWBA and GEO-MSWFA were evaluated. The adsorption isotherms parameters and thermodynamics were also determined. Detailed physical and chemical characterizations of the prepared adsorbents were carried out to further understand their impact on MB adsorption. The results from the scanning electron microscopy revealed a uniform granule-sphere like structure on both prepared geopolymers, which would facilitate the MB adsorption onto the adsorbents. The X-ray diffraction allowed observation of the microstructural transformations that occur after the alkaline activation. The surface areas of the GEO-MSWBA and the GEO-MSWFA were recorded as 32.78 m2/g and 4.5 m2/g, respectively. From the Fourier transform infrared, a stretching vibration of the aluminosilicate tetrahedral was observed, which indicated the success of geopolymerization. The prepared geopolymers showed a high capability of MB adsorption from an aqueous solution. The adsorption process was best suited and explained using the Langmuir isotherm model with a maximum adsorption capacity of 666.7 mg/g for the GEO-MSWBA (at 25°C) and 769.2 mg/g for the GEO-MSWFA (at 35°C). The positive value of the enthalpy (ΔHo) for the GEO-MSWBA suggested the reaction favored endothermic reaction while the negative value of entropy (ΔSo) indicated a solid/liquid random interaction. On the other hand, the negative ΔHo value for the GEO-MSWFA indicated the reaction followed an exothermic reaction causing energy to be released, the positive ΔSo value indicated a good affinity at the solid-liquid surface. The overall negative value for Gibbs free energy (ΔGo) for both adsorbents suggested the adsorption was spontaneous and feasible. It was also inferred that n- π interaction, direct and indirect hydrogen bond, and electrostatic interaction between the MB and the prepared geopolymers facilitated the adsorption process. The current study shows that the GEO-MSWBA and the GEO-MSWFA have a great potential of removing MB as a cationic dye from water without performing any sort of laborious pretreatments., Competing Interests: OEH is affiliated with Qatar Company: Domestic Solid Waste Management Centre (DSWMC) – Doha, State of Qatar. This does not alter our adherence to PLOS ONE policies on data or materials sharing.

Application of microemulsion modified raw date pits as an inexpensive solid extractant for removing methylene blue (MB), copper ion (Cu(2+)) and cadmium ion (Cd(2+)) has been presented. The results summarised herein are also part of an investigation conducted to evaluate the adsorption capacity by taking into consideration the experimental parameters such as pH, particle size and initial solute concentration. The experimental data obtained from the adsorption isotherms studies were used to find pollutants distribution factors and modelled using both Langmuir and Freundlich equations. The modified adsorbent was more effective toward all pollutants with high removal capacities (50-350 mg/g) and with very large distribution values (9-235 L/g) which indicates the suitability of this new material for extraction organic and inorganic pollutants. After microemulsion modification, the FTIR scans of the samples show clear differences in the position and intensity the characteristics bands of the raw date pits (RDP). Three mechanisms of the MB, Cu(2+) and Cd(2+) adsorption onto μE-MDP are possible: (i) adsorption by an electrostatic force of the anionic head group of the surfactant and the positive charge of the dye (MB+) or the metal ions (Cu(2+) or Cd(2+)), (ii) adsorption by tail groups of the surfactant and the hydrophobic character of the MB molecules. The MB is a basic dye and has basic characteristics and therefore is expected to interact strongly with the anionic head groups of the surfactants (RCOO-). In the contrary, the Cu(2+) and Cd(2+) ions are not expected to interact by the tail groups of the surfactant where the ionic radii of these ions may explain the differences between Cu(2+) (0.72 Å) and Cd(2+) (0.99 Å) adsorption capacities and (iii) filling the channel (pores) of the RDP by dissolving in the microemulsion micelles., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The investigations into structural changes which occur during adsorbent modification and the adsorption mechanisms are essential for an effective design of adsorption systems. Manganese oxides were impregnated onto diatomite to form the type known as δ-birnessite. Initial investigations established the effectiveness of manganese oxides-modified diatomite (MOMD) to remove basic and reactive dyes from aqueous solution. The adsorption capacity of MOMD for methylene blue (MB), hydrolysed reactive black (RB) and hydrolysed reactive yellow (RY) was 320, 419, and 204mg/g, respectively. Various analytical techniques were used to characterise the structure and the mechanisms of the dye adsorption process onto MOMD such as Fourier transform infrared (FTIR), X-ray diffraction (XRD) and atomic absorption spectrometry (A.A.). A small shift to higher values of the d-spacing of dye/MOMD was observed indicating that a small amount of the dye molecules were intercalated in the MOMD structure and other molecules were adsorbed on the external surface of MOMD. Two mechanisms of dye adsorption onto MOMD were proposed; intercalation of the dye in the octahedral layers and adsorption of the dye on the MOMD external surface. Moreover, the results demonstrated that the MOMD structure was changed upon insertion of MB and RY with an obvious decrease in the intensity of the second main peak of the MOMD X-ray pattern. [Copyright &y& Elsevier]

In the current study, the mechanistic understanding of the adsorption isotherm and thermodynamic aspects of cationic methylene blue (MB) dye adsorption onto cellulosic olive stones biomass from wastewater were investigated. The batch adsorption of MB onto the olive stones (black and green olive stones) was tested at a variety of pH, dye concentrations, temperatures, and biomass particle sizes. The adsorption thermodynamics such as Gibbs free energy, enthalpy, and entropy changes were also calculated. Moreover, the desorption studies of MB from the spent olive stones were studied to explore the re-usability of the biomasses. The results revealed that under the optimum pH of 10, the maximum MB uptake was achieved i.e. 80.2% for the green olive stones and 70.9% for the black olive stones. The green olive stones were found to be more efficient in remediating higher MB concentrations from water than the black olive stones. The highest MB removal of the green olive stones was achieved at 600 ppm of MB, while the highest MB removal of the black olive stones was observed at 50 ppm of MB. Furthermore, for almost all the concentrations studied (50–1000 ppm), the MB adsorption was the highest at the temperature of 45 °C (P value < 0.05). It was shown by the Fourier transform infrared that the electrostatic interaction and hydrogen bonding were proposed as dominant adsorption mechanisms at basic and acidic pH, respectively. While the hydrophobic-hydrophobic interaction was a dominant mechanism at neutral pH. The thermodynamic studies revealed that the adsorption process was endothermic, spontaneous, and favorable. Moreover, the real wastewater experiment and the desorption studies showed that the green and black olive stones were a cost-effective and promising adsorbents for MB remediation from wastewater on account of their high adsorption and desorption removal capacities. [ABSTRACT FROM AUTHOR]

Highlights: [•] Competitive sorption of two cationic dyes of significant spectral overlapping is studied using MVC. [•] Simultaneous determination of two dyes (spectral overlap 96.4%) is achieved using PLS1. [•] Irregular L2-isotherm shape was observed for dyes sorption in binary systems. [•] Langmuir model was found applicable for presenting competitive sorption of cationic dyes. [•] Competitive sorption process of cationic dyes was found exothermic and spontaneous. [Copyright &y& Elsevier]