Primary Iron- and Manganese-Carbonate Deposition in the Palaeoproterozoic Hotazel Formation, South Africa, and Implications for the Great Oxidation Event

Abstract:

The Palaeoproterozoic Hotazel Formation in the Transvaal Supergroup of South Africa represents an unusual sequence of banded iron formation interbedded with Mn-rich layers, in the form of three sedimentary cycles. The sequence has been interpreted as the product of cyclic Fe and Mn deposition in a marine environment that post-dated the first major event of atmosphere oxygenation at ~2.3Ga, known as Great Oxidation Event (GOE), despite the fact that geochronological constrains for the Hotazel rocks are still conjectural. The Hotazel deposits are thought to represent the products of anaerobic redox processes involving organic carbon and high-valence Fe/Mn-precursor species in the diagenetic environment; key evidence for such processes is provided by the low δ¹³C values of Fe- and Mn-rich carbonates contained in the Hotazel rocks (average δ¹³C: -9.6 per mil), which also typify other BIFs of the world. Here we show that the bulk carbonate fraction of the Hotazel Formation displays characteristically invariant carbon isotope signatures across large portions of the stratigraphy, irrespective of changes in bulk modal mineralogy, carbonate mineral chemistry, bulk Fe/Mn ratio or oxidation state of the rocks. This is inconsistent with traditional diagenetic models and points to a common and isotopically homogeneous source of dissolved carbon for carbonate formation in the Hotazel strata. The possibility emerges that the carbonate fraction in the Hotazel rocks initially precipitated as primary particles out of the ambient oceanic water-column, in response to processes of organic carbon cycling by Fe(III) and possibly Mn(IV) oxy-hydroxide species generated at the photic zone. Such a model precludes major atmosphere and shallow ocean oxygenation as a driver for primary oxide formation at post-GOE times, and suggests that the Hotazel deposits may in fact represent a highly evolved – chemically, isotopically and possibly biologically – marine environment that predated the GOE.