A very low concentration of manganese (Mn) in water is a critical issue for municipal and industrial water supply systems. Mn removal technology is based on the use of manganese oxides (MnOx), especially manganese dioxide (MnO2) polymorphs, under different conditions of pH and ionic strength (water salinity). The statistical significance of the impact of polymorph type (akhtenskite ε-MnO2, birnessite δ-MnO2, cryptomelane α-MnO2 and pyrolusite β-MnO2), pH (2–9) and ionic strength (1–50 mmol/L) of solution on the adsorption level of Mn was investigated. The analysis of variance and the non-parametric Kruskal–Wallis H test were applied. Before and after Mn adsorption, the tested polymorphs were characterized using X-ray diffraction, scanning electron microscope techniques and gas porosimetry analysis. Here we demonstrated the significant differences in adsorption level between MnO2 polymorphs’ type and pH; however, the statistical analysis proves that the type of MnO2 has a four times stronger influence. There was no statistical significance for the ionic strength parameter. We showed that the high adsorption of Mn on the poorly crystalline polymorphs leads to the blockage of micropores in akhtenskite and, contrary, causes the development of the surface structure of birnessite. At the same time, no changes in the surfaces of cryptomelane and pyrolusite, the highly crystalline polymorphs, were found due to the very small loading by the adsorbate.
The removal of hazardous heavy metals that have been released into the environment due to industrial activities has become an important issue in recent years. The presented study concerned the removal of copper(II) ions from aqueous solutions using dolomites. Dolomite is a very attractive adsorbent due to its wide availability, low cost, good adsorption, and environmental compatibility. The paper describes the properties of D-I and D-II dolomites from two different open-cast mines in Poland. The properties of natural adsorbents were determined based on point of zero charges (PZC), elemental analysis of the adsorbent composition, FT-IR, XRD, and SEM spectra analysis. Depending on the initial concentration of the solution used, the adsorption efficiency of copper(II) ions was 58–80% for D-I and 80–97% for D-II. The adsorption mechanism in the case of D-II dolomite was mainly based on ion exchange, while chemisorption dominated the D-I dolomite surface. Considering the possibility of the regeneration and reuse of the adsorbent, dolomite D-II is a better material (the desorption efficiency of copper(II) ions was 58–80%). The adsorption behavior of dolomites has been described using six adsorption isotherms. The best fit was obtained for the Redlich–Peterson, Jovanović, and Langmuir isotherms, indicating that monolayer adsorption occurred. The maximum adsorption capacity for copper(II) was 378 mg/g of D-I and 308 mg/g of D-II.
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