Systematic Evaluation for the Impact of the Geological Conditions on the Adsorption Affinities of Calcite as an Adsorbent of Zn2+ Ions from Aqueous Solutions: Experimental and Theoretical Studies

Abstract

Three samples of calcite (calcite crystal (CA), calcite of limestone (L.CA), and metamorphosed calcite (marble) (M.CA)) were assessed as adsorbents of Zn (II) to consider the impact of the different geological conditions. The three samples exhibit remarkable changes in their Zn (II) retention capacities (Qsat = 384.6 mg/g (CA), 274.5 mg/g (L.CA), and 512.6 mg/g (M.CA)). The retention systems of the three calcite samples were described on the basis of the suggested statistical physics-based equilibrium studies as well as the traditional kinetic and isotherm models. However, the M.CA samples exhibited the best retention capacity, the steric properties reflecting a higher active site density of CA (Nm (Zn) = 113.46 mg/g) than both M.CA (Nm (Zn) = 82.8 mg/g) and L.CA (Nm (Zn) = 52.4 mg/g) at 323 K. This was assigned to the controlling effect of the sequestered numbers of Zn (II) per site on the surfaces of the calcite phase (n(Zn) = 3.39 (CA), 5.24 (L.CA), and 6.19 (M.CA)) in addition to the higher surface area and ion exchange of the metamorphosed and deformed M.CA. The previous n(Zn) values suggested the retention of Zn (II) by a multi-ionic mechanism in a vertical orientation. The Gaussian energies (8 to 16 KJ/mol) and retention energies (˂40 KJ/mol) of Zn (II) by CA and L.CA suggested complex physical and weak chemical mechanisms involving ion exchange, hydrogen bonding, dipole bonding forces, electrostatic attractions, and van der Waals forces. The thermodynamic properties were illustrated on the basis of the internal energy, free enthalpy, and entropy functions, which validate the endothermic and spontaneous nature of the Zn (II) retention system by the three calcite samples.