Aqueous solubility of Zn incorporated into Mg-Al-layered double hydroxides

Abstract

Hydrotalcite minerals are layered double hydroxides (LDH) which play an important role in immobilizing hazardous compounds to decontaminate industrial wastewaters. The stability of an LDH is mostly evaluated in terms of its low solubility in water. However, the solubility of divalent trace metals immobilized by Mg-Al-type LDHs is not well known. Hydrotalcites containing Zn in solid solution, (Mg+Zn)3-Al-LDH, were synthesized by alkaline co-precipitation. A series of eleven LDH phases with Zn mole fractions XZn = Zn/(Mg+Zn) of 0–1 were characterized by powder X-ray diffractometry (XRD), Fourier-transform infrared (FTIR) spectroscopy, thermogravimetry (TGA), scanning and transmission electron microscopy (SEM/TEM), Brunauer-Emmett-Teller (BET) surface area analysis, and inductively coupled plasma mass (ICP-MS) spectrometry. The XRD analysis provided sharp characteristic spacings for d003 and d006 which occurred for all samples, confirming a layered LDH structure. Cell parameters (a, c) obeyed Vegard’s law and confirmed the formation of a regular solid-solution series without a mixing gap. An aqueous equilibrium time was determined by kinetic dissolution experiments. Steady-state solubility occurred after 120 days, but the experiments continued up to 240 days. The XRD and SEM/TEM analyses indicated no phase changes during the long-term dissolution experiments; neither were phase impurities detected after 240 days. The solubility products of the Mg- and Zn-bearing endmember compositions were calculated from experimentally determined total cation and anion concentrations using the Visual Minteq code for considering element speciation and ion pairing. The solubility product decreased as the Zn mole fraction increased, suggesting that the Zn-bearing LDH phases were more stable than the pure Mg3-Al-LDHs. Solid-solution aqueous-solution thermodynamic equilibrium modeling using the Lippmann “total solubility product” approach and applying Lippmann diagrams with logarithmic x-axes revealed a log-linear decrease in aqueous Zn solubility. The results are promising for remediation of metal-bearing liquid wastes because the metals that co-precipitated with the LDH were more strongly retained and, therefore, less soluble than the hydroxides or carbonates of the trace metal.