Birnessite: A New Oxidant for Green Rust Formation

Iron and manganese are ubiquitous in the natural environment. Fe(II)-Fe(III) layered double hydroxide, commonly called green rust (GR), and Mn(III)-Mn(IV) birnessite (Bir) are also well known to be reactive solid compounds. Therefore, studying the chemical interactions between Fe and Mn species could contribute to understanding the interactions between their respective biogeochemical cycles. Moreover, ferromanganese solid compounds are potentially interesting materials for water treatment. Here, a {Fe(OH)(2), Fe(II)(aq)} mixture was oxidized by Bir in sulphated aqueous media in the presence or absence of dissolved O(2). In oxic conditions for an initial Fe(II)/OH(−) ratio of 0.6, a single GR phase was obtained in a first step; the oxidation kinetics being faster than without Bir. In a second step, GR was oxidised into various final products, mainly in a spinel structure. A partial substitution of Fe by Mn species was suspected in both GR and the spinel. In anoxic condition, GR was also observed but other by-products were concomitantly formed. All the oxidation products were characterized by XRD, XPS, and Mössbauer spectroscopy. Hence, oxidation of Fe(II) species by Bir can be considered as a new chemical pathway for producing ferromanganese spinels. Furthermore, these results suggest that Bir may participate in the formation of GR minerals.