Authigenic anatase within 1 billion-year-old cells.

ABSTRACT

The siliciclastic ~1 Ga-old strata of the Torridon Group, Scotland, contain some of the most exquisitely preserved three-dimensional organic-walled microfossils (OWMs) of the Precambrian. A very diverse microfossil assemblage is hosted in a dominantly phosphatic and clay mineral matrix, within the Diabaig and the Cailleach Head (CH) Formations. In this study, we report on several microfossil taxa within the CH Formation (Leiosphaeridia minutissima, Leiosphaeridia crassa, Synsphaeridium spp. and Myxococcoides spp.) that include populations of cells containing an optically transparent and highly refringent mineral, here identified using electron microscopy as anatase (TiO2 ). Most anatase crystals occur entirely within individual cells, surrounded by unbroken carbonaceous walls. Rarely, an anatase crystal may protrude outside a cell, interpreted to correspond to zones where the cell wall had broken down prior to anatase precipitation. Where an anatase crystal entombs an organic intracellular inclusion (ICI), the ICI is large and well preserved. These combined observations indicate that the intracellular anatase is an authigenic sedimentary phase, making this the first report of in situ precipitated anatase intimately associated with microfossils. The ability of anatase to preserve relatively large volumes of intracellular and cell wall organic material in these cells suggests that the crystallisation of anatase entombed cellular contents particularly quickly, soon after the death of the cell. This is consistent with the strong affinity of Ti for organic material, the low solubility of TiO2 , and reports of Ti occurring in living organisms. With the data currently available, we propose a mineralisation pathway for anatase involving Ti complexation with organic ligands within specific cells, leading to localised post-mortem anatase nucleation inside these cells as the complexes broke down. Further overgrowth of the anatase crystals was likely fuelled by very early diagenetic mobilisation of Ti that had been bound to more labile organic material nearby in the sediments.