This study reports the valorization of pistachio shell agricultural waste, aiming to develop an eco-friendly and cost-effective biosorbent for cationic brilliant green (BG) dye adsorption from aqueous media. Pistachio shells were mercerized in an alkaline environment, resulting in the treated adsorbent (PSNaOH). The morphological and structural features of the adsorbent were analyzed using scanning electron microscopy, Fourier transform infrared spectroscopy, and polarized light microscopy. The pseudo-first-order (PFO) kinetic model best described the adsorption kinetics of the BG cationic dye onto PSNaOH biosorbents. In turn, the equilibrium data were best fitted to the Sips isotherm model. The maximum adsorption capacity decreased with temperature (from 52.42 mg/g at 300 K to 46.42 mg/g at 330 K). The isotherm parameters indicated improved affinity between the biosorbent surface and BG molecules at lower temperatures (300 K). The thermodynamic parameters estimated on the basis of the two approaches indicated a spontaneous (ΔG < 0) and exothermic (ΔH < 0) adsorption process. The design of experiments (DoE) and the response surface methodology (RSM) were employed to establish optimal conditions (sorbent dose (SD) = 4.0 g/L and initial concentration (C0) = 10.1 mg/L), yielding removal efficiency of 98.78%. Molecular docking simulations were performed to disclose the intermolecular interactions between the BG dye and lignocellulose-based adsorbent.
Herein, we report the performance of some low-cost biosorbents developed by environment-friendly modification of walnut shells. Two types of biosorbents were prepared by ecological modification of walnut shell surfaces: (1) biosorbents obtained by hot water treatment (WSH2O) and (2) biosorbents produced by mercerization (WSNaOH). Different techniques were used to evaluate the morphological, elemental, and structural modification of the biosorbents, by comparison with raw materials. These characterization techniques involved scanning electron microscopy (SEM) coupled with energy-dispersive X-ray analysis, and Fourier-transform infrared spectroscopy (FTIR). The biosorbents were employed for the removal of methylene blue (MB) and crystal violet (CV) cationic dyes (as model organic pollutants) from aqueous solutions. The kinetic adsorption data mainly followed the pseudo-first-order model. The maximum adsorption capacities of the produced biosorbents ranged from 102 to 110 mg/g and were observed at 330 K. Equilibrium data for adsorption were fitted to Langmuir and Freundlich isotherm models. The calculated values of thermodynamic parameters suggested that the investigated adsorption processes were exergonic (ΔG < 0) and exothermic (ΔH < 0). In addition, a possible valorization of the cost-effective and eco-friendly spent biosorbents was tested by performing secondary adsorption of the anionic dyes.
During a study aiming to recover strategic elements and minerals from coal fly ash and bottom ash (RAREASH and CHARPHITE projects funded, respectively, by the 2nd ERA-MIN and 3rd ERA-MIN Programs of the European Union Commission), it was found that in coal fly ash and bottom ash from Romania and Poland, several morphotypes did not fit into the general fly ash classifications, unless grouped together as “undifferentiated inorganics”. However, the combination of reflected light optical microscopy under oil immersion, scanning electron microscopy, and X-ray microanalysis (SEM/EDS) showed that many of these morphotypes not only have distinctive petrographic patterns but are also characterized by a chemical assemblage dominated by Ca, Mg, and P. In this paper, a survey of the literature is presented together with several detailed studies of samples from the RAREASH and CHARPHITE projects from which the following nomenclature are proposed: “calcispheres” for spongy Ca-rich morphotypes, “calcimagnesiaspheres” for (Ca + Mg)-rich morphotypes with visible MgO nodules and/or periclase (MgO) exsolved from Ca aluminate-silicate glass, and “magnesiaspheres” divided into “magnesiaferrospheres” for (Mg + Fe)-rich morphotypes with magnesioferrite, and “magnesiaoxyspheres” for magnesiaspheres mainly composed of (Mg + Fe)-rich amorphous material with visible MgO nodules and/or periclase.
Coal ash char concentrates from four countries (Portugal, Poland, Romania, and South Africa) were prepared, characterised, and graphitized under the scope of the Charphite project (Third ERA-MIN Joint Call (2015) on the Sustainable Supply of Raw Materials in Europe). Coal ash chars may be a secondary raw material to produce synthetic graphite and could be an alternative to natural graphite, which is a commodity with a high supply risk. The char concentrates and the graphitized material derived from the char concentrates were characterised using proximate analysis, X-ray fluorescence, X-ray diffraction (structural), Raman microspectroscopy, solid-state nuclear magnetic resonance, scanning electron microscopy, and petrographic analyses to determine if the graphitization of the char was successful, and which char properties enhanced or hindered graphitization. Char concentrates with a lower proportion of anisotropic particles and a higher proportion of mixed porous particles showed greater degrees of graphitization. It is curious to see that embedded Al2O3 minerals, such as glass and clay, influenced graphitization, as they most likely acted as catalysts for crystal growth in the basal direction. However, the graphitized samples, as a whole, do not compare well against a reference natural graphite sample despite some particles in select char concentrates appearing to be graphitized following graphitization.
The livestock sector is one of the most important sectors of the agricultural economy due to an increase in the demand for animal protein. This increase generates serious waste disposal concerns and has negative environmental consequences. Furthermore, the food production chain needs phosphorus (P), which is listed as a critical raw material due to its high demand and limited availability in Europe. Manure contains large amounts of P and other elements that may be recycled, in the frame of circular economy and “zero waste” principles, and reused as a by-product for fertilizer production and other applications. This paper focuses on the extraction and recovery of amorphous silica from rice husk poultry litter ash. Two different extraction procedures are proposed and compared, and the obtained silica is characterized. This work shows that amorphous silica can be recovered as an almost pure material rendering the residual ash free of P. It also addresses the possibility of more specific phosphorous extraction procedures via acid leaching.
Nowadays, very coarse wool fibers are considered waste biomass and are discarded at random or burned. Therefore, it is of actual interest to valorize coarse wool fibers as utile products. In this sense, we report herein an environmentally-friendly process for the preparation of a new material based on oxidized wool fibers and designed for efficient adsorption of heavy metals from wastewater. The morphology and the structure of the obtained product were characterized by scanning electron microscopy (SEM) coupled with an X-ray energy-dispersive module (EDX) and by Fourier-transform infrared spectroscopy (FTIR). Likewise, the performances of the oxidized wool fibers for the adsorption of heavy metal cations (Cu2+, Cd2+, Pb2+) from aqueous solutions were tested. The adsorption kinetics data were analyzed by applying the pseudo-first-order (PFO) and pseudo-second-order (PSO) kinetic models. The equilibrium of the adsorption process was investigated by using the Freundlich and Langmuir isotherm models. According to the Langmuir isotherms registered at 300 K, the maximum adsorption capacities of the oxidized wool were found to increase from Cu2+ (9.41 mg/g) and Cd2+ (10.42 mg/g) to Pb2+ (30.71 mg/g). Consequently, the removal efficiency of metal ions was found to vary in the range of 96.8–99.7%. The thermodynamic parameters (e.g., enthalpy, entropy, and Gibbs free energy) were calculated and discussed.