Retention of aqueous Ba2+ ions by calcite and aragonite over a wide range of concentrations: Characterization of the uptake capacity, and kinetics of sorption and precipitate formation

Abstract

The uptake of aqueous Ba2+, ions by abiogenic calcite and aragonite was studied over a wide range of concentration; 1.0 × 101, 5.0 × 101, 1.0 × 102 5.0 × 102, 1.0 × 103, 5.0 × 104, and 1.0 × 104 mg/L. The uptake process was characterized using ICP-AES, XRPD, SEM/EDS, and FTIR techniques. Up to the initial concentration of 5.0 × 102 mg/L, the uptake of Ba2+ ions was fast and obeyed Lagergren's kinetic model. The equilibrium data were adequately described using Freundlich isotherm model. The overgrowth of BaCO3 (witherite) took place at higher concentrations, in a kinetically slow process and enhanced the uptake of Ba2+ ions. Quantitative XRPD was used to evaluate the fractions of precipitated BaCO3 on calcite and aragonite minerals and monitor their variation with time. At all the studied concentrations, aragonite showed higher removal capacity of Ba2+ and faster uptake kinetics than did calcite. The precipitated crystals appeared to predominantly possess olivary-like morphology with an average particle size of 1-2 μm. EDS was used to reveal the elemental quantities of Ba and Ca after BaCO3 formation on calcite and aragonite surfaces. FTIR spectroscopy was employed to analyze the vibrational modes in carbonate mixtures upon incorporation of Ba2+ by sorption and precipitation mechanisms.