Important role of pore-filling mechanism in separating naproxen from water by micro-mesoporous carbonaceous material.

Commercial micro-mesoporous carbonaceous material (MCM; 56.8% mesopores) was applied for investigating the removal phenomenon of naproxen drug in aqueous solutions through batch adsorption experiments. Results demonstrated that the adsorption capacity of MCM to naproxen was slightly affected by different pHeq (2.0-11) and ionic strength (0-1 M NaCl). Adsorption kinetics, isotherms, thermodynamics, and mechanisms were evaluated at pH 7.0. Adsorption kinetics indicated the rate constants for adsorption (0.2 × 10-3  L/(mg × min) and desorption (0.076/min) and the adsorption equilibrium constant (2.6 × 10-3  L/mg). Adsorption isotherm showed that MCM exhibited a high-affinity adsorption capacity to naproxen (even at low concentrations) and its Langmuir maximum adsorption capacity (Qmax ) was 252.7 mg/g at 25°C. Adsorption thermodynamics proved that the adsorption process was endothermic and physisorption (ΔH° = 9.66 kJ/mol). The analysis result of pore size distribution demonstrated that the internal pore structure of MCM was appropriate for adsorbing naproxen molecules. Pore-filing mechanism (pore diffusion phenomenon) was confirmed by a considerable decrease in BET-surface area (585 m2 /g) and total pore volume (0.417 cm3 /g) of MCM after adsorbing naproxen (~1000 mg/L and pH 7.0) at 5 min (341 and 0.256), 60 min (191 and 0.205), 120 min (183 and 0.193), 360 min (144 and 0.175), and 24 h (71.6 m2 /g and 0.123 cm3 /g, respectively). The pore diffusion occurred rapidly (even at the initial adsorption period of 5 min). The FTIR technique was applied to identify the existence of C-H···π and n-π interaction. π-π interaction (evaluated through ID /IG ratio and C=C band) played a minor contribution in adsorption mechanisms. The ID /IG ratio (determined by the Raman technique) of MCM before adsorption (1.195) was similar to that after adsorption (1.190), and the wavenumber (C=C band; its FTIR spectrum) slightly shifted from 1638 to 1634 cm-1 after adsorption. A decrease in the Qmax value of MCM from 249 to 217 (H2 O2 -oxidized MCM) or to 224 mg/g (HNO3 -oxidized MCM) confirmed the presence of π-π interaction. Electrostatic attraction was a minor contribution. MCM can serve as a promising material for removing naproxen from water environment through a pore-filling mechanism. PRACTITIONER POINTS: Pore-filling mechanism was proposed by comparing textural properties of MCM before and after adsorbing naproxen. C-H···π and n-π interactions were identified via FTIR technique. π-π interaction was observed by FTIR and Raman techniques. Oxidation of MCM with HNO3 or H2 O2 was a helpful method to explore π-π interaction. Electrostatic attraction was explained through studies: effects of pH and NaCl along with desorption.

Peanut shells-derived biochars prepared from different carbonization processes: Comparison of characterization and mechanism of naproxen adsorption in water.

The ubiquitous appearance of nonsteroidal anti-inflammatory drugs (i.e., naproxen) in water bodies has raised enormous concerns among general public. Development of promising materials for eliminating such contaminants from water environment has attracted much attention in the scientific community. In this study, three (direct, post-treated and pre-treated) methods were developed to prepare biochars (800-PSB, 800-800-PSB, and 190-800-PSB, respectively) derived from the wastes of peanut shells (PS). They were thoroughly characterized by various important properties (i.e., porosity and superficial functional group) and applied to remove naproxen drug from water. Results indicated that although the pre- and post-treatments had a slight effect on the surface area of biochars (i.e., 571 m2/g for 800-PSB, 596 m2/g for 800-800-PSB, and 496 m2/g for 190-800-PSB), such treatments remarkably improved the adsorption capacity of biochar. The maximum adsorption capacity of biochar (obtained from the Langmuir model) towards naproxen in solution at 25 decreased in the following order: 800-800-PSB (324 mg/g) > 190-800-PSB (215 mg/g) > 800-PSB (105 mg/g). The thermodynamic study demonstrated that the adsorption was spontaneous and exothermic. Depending the preparation process, the contribution of each mechanism in the adsorption process was dissimilar. The overall adsorption mechanism was regarded as pore filling, π-π interaction, hydrogen bonding formations, n-π interaction, van der Waals force, and electrostatic attraction. Two methods used to identify the important role of π-π interaction were proposed herein. The possible desorption and reuse of laden-biochars were investigated by the chemical and thermal methods. The prepared biochar samples can serve as potential carbonaceous porous adsorbents for effectively removing naproxen from water media.

Separation and Preconcentration of Nickel(II) from Drinking, Spring, and Lake Water Samples with Amberlite CG-120 Resin and Determination by Flame Atomic Absorption Spectrometry.

In this study, Amberlite CG-120 adsorbent was used for the separation/preconcentration of Ni(II) ions in commercial drinking, spring and lake water samples before detection by flame atomic absorption spectrometry. Various optimization parameters for Ni(II) determination, such as pH, eluent type and concentration, sample and eluent flow rates, amount of adsorbent, were investigated to obtain better sensitivity, accuracy, precision and quantitative recovery. Furthermore, the interference effects of some ions on the recovery efficiency of Ni(II) were also investigated. The optimum experimental parameters were obtained in the case of pH 1; 5 mL of 4 mol L-1 HCl for eluent and 0.3 g for the adsorbent amount. The limit of detection was found to be 0.58 µg L-1 and linearity ranged from 5 to 50 µg L-1. The accuracy of the method was tested by the certified reference material of TMDA-70.2 Ontario Lake Water at a 95% confidence level.