Evidence for aqueous clusters as intermediates during zinc sulfide formation

Using zinc sulfide as an example, we demonstrate a plausible stepwise process for the formation of minerals from low temperature aqueous solutions. The process occurs with the formation of soluble complexes that aggregate into soluble rings and clusters. The final moiety in solution has a structure similar to the moiety in the first formed solid, which is a restatement of the Ostwald step rule. Titrations of aqueous Zn(II) with bisulfide indicate that sulfide clusters form at concentrations of 20 mu M (or less) of metal and bisulfide. Precipitation does not occur according to voltammetric measurements using a mercury electrode and UV-VIS (ultra-violet to visible) spectroscopic data. UV-VIS data and filtration experiments indicate that the material passes through 0.1 mu m Nuclepore and 1000 dalton filters. The complexes form rapidly (k(f) > 10(8) Ms-1), are kinetically inert to dissociation and thermodynamically strong. Although a neutral complex of 1:1 (ZnS) empirical stoichiometry initially forms, an anionic complex with an empirical 2 Zn:3 S stoichiometry results with continued addition of sulfide. Gel electrophoresis confirms the existence of a cluster that is negatively charged with a molecular mass between 350 and 750 daltons. On the basis of known mineral and thiol complex structures for these systems, a tetrameric cluster unit of Zn4S6(H2O)(4)(4-) is likely. Molecular mechanic calculations show that this cluster is structurally analogous to ZnS minerals (particularly sphalerite) and is a viable precursor to mineral formation and a product of mineral dissolution. The formation of Zn4S6(H2O)(4)(4-) can occur from condensation of Zn3S3(H2O)(6) rings, which are neutral molecular clusters. The Zn atoms on one Zn3S3(H2O)(6) ring combine with the S atoms on another Zn3S3(H2O)(6) to lead to higher order clusters with loss of water. The Zn4S64- species form by the cross-linking of two neutral Zn,S, rings by added sulfide; thus a Zn-S-Zn bridge forms across the rings with subsequent rearrangement and condensation to Zn4S64-; this combination results in a sphalerite-like cluster. if the rings condense without additional sulfide, a wurtzite-like structure could form. All condensations result in sulfide displacement of water from Zn to form Zn-S bonds. Water loss is an example of an entropy-driven process, which leads to a more favorable thermodynamic process. These clusters would be resistant to oxidation by O-2. Voltammetric: experiments indicate neutral and anionic clusters for Zn and agree with ion chromatographic data from the sulfidic waters of the Black Sea. Copyright (C) 1999 Elsevier Science Ltd.