Mesoproterozoic surface oxygenation accompanied major sedimentary manganese deposition at 1.4 and 1.1 Ga.

Manganese (Mn) oxidation in marine environments requires oxygen (O2 ) or other reactive oxygen species in the water column, and widespread Mn oxide deposition in ancient sedimentary rocks has long been used as a proxy for oxidation. The oxygenation of Earth's atmosphere and oceans across the Archean-Proterozoic boundary are associated with massive Mn deposits, whereas the interval from 1.8-1.0 Ga is generally believed to be a time of low atmospheric oxygen with an apparent hiatus in sedimentary Mn deposition. Here, we report geochemical and mineralogical analyses from 1.1 Ga manganiferous marine-shelf siltstones from the Bangemall Supergroup, Western Australia, which underlie recently discovered economically significant manganese deposits. Layers bearing Mn carbonate microspheres, comparable with major global Mn deposits, reveal that intense periods of sedimentary Mn deposition occurred in the late Mesoproterozoic. Iron geochemical data suggest anoxic-ferruginous seafloor conditions at the onset of Mn deposition, followed by oxic conditions in the water column as Mn deposition persisted and eventually ceased. These data imply there was spatially widespread surface oxygenation ~1.1 Ga with sufficiently oxic conditions in shelf environments to oxidize marine Mn(II). Comparable large stratiform Mn carbonate deposits also occur in ~1.4 Ga marine siltstones hosted in underlying sedimentary units. These deposits are greater or at least commensurate in scale (tonnage) to those that followed the major oxygenation transitions from the Neoproterozoic. Such a period of sedimentary manganogenesis is inconsistent with a model of persistently low O2 throughout the entirety of the Mesoproterozoic and provides robust evidence for dynamic redox changes in the mid to late Mesoproterozoic.

Metalliferous Biosignatures for Deep Subsurface Microbial Activity.

The interaction of microbes and metals is widely assumed to have occurred in surface or very shallow subsurface environments. However new evidence suggests that much microbial activity occurs in the deep subsurface. Fluvial, lacustrine and aeolian 'red beds' contain widespread centimetre-scale reduction spheroids in which a pale reduced spheroid in otherwise red rocks contains a metalliferous core. Most of the reduction of Fe (III) in sediments is caused by Fe (III) reducing bacteria. They have the potential to reduce a range of metals and metalloids, including V, Cu, Mo, U and Se, by substituting them for Fe (III) as electron acceptors, which are all elements common in reduction spheroids. The spheroidal morphology indicates that they were formed at depth, after compaction, which is consistent with a microbial formation. Given that the consequences of Fe (III) reduction have a visual expression, they are potential biosignatures during exploration of the terrestrial and extraterrestrial geological record. There is debate about the energy available from Fe (III) reduction on Mars, but the abundance of iron in Martian soils makes it one of the most valuable prospects for life there. Entrapment of the microbes themselves as fossils is possible, but a more realistic target during the exploration of Mars would be the colour contrasts reflecting selective reduction or oxidation. This can be achieved by analysing quartz grains across a reduction spheroid using Raman spectroscopy, which demonstrates its suitability for life detection in subsurface environments. Microbial action is the most suitable explanation for the formation of reduction spheroids and may act as metalliferous biosignatures for deep subsurface microbial activity.

Early oxygenation of the terrestrial environment during the Mesoproterozoic.

Geochemical data from ancient sedimentary successions provide evidence for the progressive evolution of Earth's atmosphere and oceans. Key stages in increasing oxygenation are postulated for the Palaeoproterozoic era (∼2.3 billion years ago, Gyr ago) and the late Proterozoic eon (about 0.8 Gyr ago), with the latter implicated in the subsequent metazoan evolutionary expansion. In support of this rise in oxygen concentrations, a large database shows a marked change in the bacterially mediated fractionation of seawater sulphate to sulphide of Δ(34)S < 25‰ before 1 Gyr to ≥50‰ after 0.64 Gyr. This change in Δ(34)S has been interpreted to represent the evolution from single-step bacterial sulphate reduction to a combination of bacterial sulphate reduction and sulphide oxidation, largely bacterially mediated. This evolution is seen as marking the rise in atmospheric oxygen concentrations and the evolution of non-photosynthetic sulphide-oxidizing bacteria. Here we report Δ(34)S values exceeding 50‰ from a terrestrial Mesoproterozoic (1.18 Gyr old) succession in Scotland, a time period that is at present poorly characterized. This level of fractionation implies disproportionation in the sulphur cycle, probably involving sulphide-oxidizing bacteria, that is not evident from Δ(34)S data in the marine record. Disproportionation in both red beds and lacustrine black shales at our study site suggests that the Mesoproterozoic terrestrial environment was sufficiently oxygenated to support a biota that was adapted to an oxygen-rich atmosphere, but had also penetrated into subsurface sediment.