title: Formation of crystalline Zn-Al layered double hydroxide precipitates on γ-alumina: the role of mineral dissolution.
abstract: To better understand the sequestration of toxic metals such as nickel (Ni), zinc (Zn), and cobalt (Co) as layered double hydroxide (LDH) phases in soils, we systematically examined the presence of Al and the role of mineral dissolution during Zn sorption/precipitation on γ-Al(2)O(3) (γ-alumina) at pH 7.5 using extended X-ray absorption fine structure spectroscopy (EXAFS), high-resolution transmission electron microscopy (HR-TEM), synchrotron-radiation powder X-ray diffraction (SR-XRD), and (27)Al solid-state NMR. The EXAFS analysis indicates the formation of Zn-Al LDH precipitates at Zn concentration ≥0.4 mM, and both HR-TEM and SR-XRD reveal that these precipitates are crystalline. These precipitates yield a small shoulder at δ(Al-27) = +12.5 ppm in the (27)Al solid-state NMR spectra, consistent with the mixed octahedral Al/Zn chemical environment in typical Zn-Al LDHs. The NMR analysis provides direct evidence for the existence of Al in the precipitates and the migration from the dissolution of γ-alumina substrate. To further address this issue, we compared the Zn sorption mechanism on a series of Al (hydr)oxides with similar chemical composition but differing dissolubility using EXAFS and TEM. These results suggest that, under the same experimental conditions, Zn-Al LDH precipitates formed on γ-alumina and corundum but not on less soluble minerals such as bayerite, boehmite, and gibbsite, which point outs that substrate mineral surface dissolution plays an important role in the formation of Zn-Al LDH precipitates.
authors.affiliation: Environmental Soil Chemistry Group, Delaware Environmental Institute and Department of Plant and Soil Sciences, University of Delaware, Newark, Delaware 19717, USA. weili@udel.edu
authors.forename: Wei
authors.initials: W
authors.lastname: Li
authors.forename: Kenneth J T
authors.initials: KJ
authors.lastname: Livi
authors.forename: Wenqian
authors.initials: W
authors.lastname: Xu
authors.forename: Matthew G
authors.initials: MG
authors.lastname: Siebecker
authors.forename: Yujun
authors.initials: Y
authors.lastname: Wang
authors.forename: Brian L
authors.initials: BL
authors.lastname: Phillips
authors.forename: Donald L
authors.initials: DL
authors.lastname: Sparks
mesh_terms: D000327:Adsorption; D000535:Aluminum / Q000737:chemistry*; D000537:Aluminum Oxide / Q000737:chemistry*; D011232:Chemical Precipitation; D003460:Crystallization; D006878:Hydroxides / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D046529:Microscopy, Electron, Transmission; D008903:Minerals / Q000737:chemistry; D012995:Solubility; D056928:X-Ray Absorption Spectroscopy; D014961:X-Ray Diffraction; D015032:Zinc / Q000737:chemistry*
chemical_list: D006878:Hydroxides; D008903:Minerals; D000535:Aluminum; D015032:Zinc; D000537:Aluminum Oxide