Double hydroxide solids precipitated homogeneously from three laboratory-synthesized aqueous solutions that simulated mildly contaminated surface or groundwater. Over a limited pH range, precipitates formed rapidly from dissolved ions, and more slowly by incorporating ions dissolving from other solids, including highly soluble aluminous solids. The precipitates were characterized by size and shape via transmission electron microscopy (TEM), by composition via inductively coupled plasma-mass spectrometry (ICP-MS) of mother solutions and analytical electron microscopy (AEM) of precipitates, and by structure via powder X-ray diffraction (XRD), TEM, and extended X-ray absorption fine structure (EXAFS) spectroscopy. They were identified as nanocrystalline cobalt hydrotalcite (CoHT) of the form [Co(II)1-xAl(III)x(OH)2]x+(An−x/n)·mH2O, with x = 0.17–0.25, A = CO32−, NO3−, or H3SiO4−n = anion charge and m undetermined. Complete solid solution may exist at the macroscopic level for the range of stoichiometrics reported, but clustering of Co atoms within hydroxide layers indicates a degree of immiscibility at the molecular scale. Composition evolved toward the Co-rich endmember with time for at least one precipitate. The small layer charge in the x = 0.17 precipitate caused anionic interlayers to be incomplete, producing interstratification of hydrotalcite and brucite-like layers. Solubility products estimated from solution measurements for the observed final CoHT stoichiometries suggest that CoHT is less soluble than the inactive forms of Co(OH)2 and CoCO3 near neutral pH. Low solubility and rapid formation suggest that CoHT solids may be important sinks for Co in contact with near neutral pH waters. Because hydrotalcite can incorporate a range of transition metals, precipitation of hydrotalcite may be similarly effective for removing other trace metals from natural waters.

In bioreactor systems for the treatment of metal-contaminated water, pretreatment with zerovalent Fe can be exploited for oxygen consumption and H2 production. In this study, a column experiment is used to investigate the changes in surface chemistry and solid phase products that result from the reaction of a Zn-sulphate-lactate solution with zerovalent Fe filings. The results of this study indicate that zerovalent Fe is very effective in immobilizing dissolved Zn with a porewater residence time of 1.3 –3.1 days. A combination of X-ray diffractometry, X-ray photoelectron spectroscopy, and mineral equilibria calculations indicates that Zn precipitates as Zn(OH)2 and zincite at pH 9 –10. At pH ≈6, Zn primarily adsorbs to abundant ferric oxyhydroxides, although incorporation in green rust is also considered. During the course of the experiment, the surface mineralogy changes from magnetitelepidocrocite- goethite to green rust-akaganéite-goethite. The results suggest that the zerovalent Fe surface becomes passivated by a surface film of ferric oxyhydroxides, green rust and organic material, so that the rate of electron transfer and proton consuming reactions (i.e. oxygen consumption, H2 generation) declines, resulting in a decrease in solution pH.