Transformation of Co-containing birnessite to todorokite: Effect of Co on the transformation and implications for Co mobility

Abstract

The mobility and fate of bioessential transition metals, such as Ni and Co, are strongly controlled by their association with phyllomanganate minerals such as birnessite. These minerals however, can transform to tectomanganates such as todorokite during soil and sediment diagenesis, yet the mobility and fate of most metals during the transformation process remain largely unknown. Here this research investigates the effect of Co on, and the mobility and fate of Co during the transformation of birnessite into tunnel structure minerals. A range of Co-containing birnessite precursors with up to 16.9 % Co/(Co + Mn) molar ratios were synthesised, and subsequently transformed via a mild reflux procedure designed to mimic the diagenesis of these layered precursors into tunnel structures. The layered precursors and reflux products were characterized using a combination of mineralogical and geochemical techniques, including powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), high resolution transmission electron microscopy (HRTEM) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The results show that Co(III) is structurally incorporated into the layered precursors and reflux products, through the isomorphic substitution of Mn(III). The structural incorporation of Co(III) into the layered precursors leads to an overall reduction of Jahn-Teller distorted Mn(III) octahedra in these minerals, a key factor for their transformation to tunnel structures. As a consequence, the presence of such structural Co(III) disrupts the transformation of birnessite into todorokite, leading to the coexistence of 9.6 Å asbolane-like phyllomanganate and non-ideal 3 × n, or a-disordered, todorokite-like tectomanganates in the transformation products. Newly formed todorokite exhibits a wide range of 3 × n tunnel dimensions (n up to 13) and a plate-like morphology. Overall the structural incorporation of non Jahn-Teller distorted cations like Co(III) into birnessite might help explain the often observed predominance of phyllomanganates over tectomanganates in soils and sediments, and the persistence of phyllomanganates in ferromanganese deposits that can be many millions of years old. The results also indicate that Co(III) initially associated with birnessite is retained in the solid phase during transformation, and thus the mobility of Co(III) is limited. EXAFS data suggest that Co is mainly located in the octahedral layers of asbolane-like phyllomanganate and at non-edge sites in non-ideal todorokite. Overall the transformation of Co-containing birnessite into non-ideal todorokite and asbolane-like layered structures maintains the strong sequestration of Co by Mn oxides.