Manganese and cobalt redox cycling in laterites; Biogeochemical and bioprocessing implications

Abstract

Cobalt is essential for the modern technology that underpins the decarbonisation of our economies, but its supply is limited leading to its designation as a critical metal. Cobalt biogeochemistry is poorly understood, yet knowledge of how biogeochemical cycling impacts cobalt behaviour could assist the development of new techniques to recover cobalt from ores, and so improve the security of supply. Laterites are an important source of cobalt, they are primarily processed for nickel using energy or chemical intensive processes, with cobalt recovered as a by-product. Metal-reducing conditions were stimulated in laterite sediment microcosms by the addition of simple and cheaply available organic substrates (acetate or glucose). At the end of the experiment the amount of easily recoverable cobalt (aqueous or extractable with acetic acid) increased from < 1% to up to 64%, which closely mirrored the behaviour of manganese, while only a small proportion of iron was transformed into an easily recoverable phase. Sequencing of the microbial community showed that the addition of organic substrates stimulated the growth of indigenous prokaryotes closely related to known manganese(IV)/iron(III)-reducers, particularly from the Clostridiales, and that fungi assigned to Penicillium, known to produce organic acids beneficial for leaching cobalt and nickel from laterites, were identified. Overall, the results indicate that the environmental behaviour of cobalt in laterites is likely to be controlled by manganese biogeochemical cycling by microorganisms. These results are compelling given that similar behaviour was observed in four laterites (Acoje, Çaldağ, Piauí and Shevchenko) from different continents. A new bioprocessing strategy is proposed whereby laterites are treated with an organic substrate to generate metal-reducing conditions, then rinsed with acetic acid to remove the cobalt. Not only are organic substrates environmentally-friendly and potentially sourced from waste carbon substrates, a minimal amount of iron oxides was mobilised and consequently less waste generated.