Oolitic Ironstones, Continental Iron Flux and Reverse Weathering in the Proterozoic Eon: Insights from the Tonian Katherine Group, Yukon

Oolitic ironstones are iron-rich and chert-poor sedimentary rocks containing concentrically coated grains composed of iron (oxyhydr)oxides and iron phyllosilicates that offer a unique window into iron cycling in ancient coastal environments. These enigmatic deposits are common in the Phanerozoic stratigraphic record yet lack clear modern analogues, and curiously are thought to be absent from Precambrian strata, suggesting a secular control on their deposition. Here we describe a previously unreported ironstone from the middle Tonian (ca. 850 Ma) Katherine Group in the Wernecke Inlier (Yukon, Canada), and show that similar deposits can be found-albeit rarely-throughout the Proterozoic. We investigate the origin of this unit and evaluate its palaeoenvironmental significance, and in light of an extensive literature review, present a holistic model for Precambrian ironstone deposition. The Katherine ironstone occurs in multiple horizons in the McClure and Abraham Plains formations and contains iron ooids and oncoids composed dominantly of authigenic hematite and berthierine, with detrital quartz grains. Textural relationships demonstrate that these coated grains formed on the seafloor with synsedimentary reworking, and the fine interlamination of these phases in grain coatings suggests redox and pH fluctuation during ironstone genesis. Facies associations indicate that the ironstones accumulated in a range of low-energy, shallow marine environments (tidal mudflats and coastal embayments). Geochemical analyses offer insights into genetic processes, and the radiogenic Nd isotope composition and negative Eu anomalies of the Katherine ironstone suggest a continental iron source. We present a model whereby abundant iron, cations, and silica-requisite for the authigenesis of iron phyllosilicates-were supplied from chemical weathering and preferentially enriched in coastal environments due to gradients in pH, Eh and salinity. This continental input would have led to intense iron cycling coupled to organic matter respiration, iron phyllosilicate authigenesis (i.e., reverse weathering). The enrichment of authigenic Fe(III) (oxyhydr)oxides and Fe(II) phyllosilicates took place on a broad coastal plain influenced by both autogenic and allogenic fluctuations in relative sea level, likely in a humid, tropical climate. The lenticular and episodic nature of ironstones in the Proterozoic stratigraphic record suggests that a unique combination of environmental conditions fostered ironstone accumulation. By reviewing the literature on oolitic ironstones, we re-evaluate the temporal distribution of these deposits compared to Archaean-Palaeoproterozoic iron formations, and show that the Great Oxidation Event may have been a prerequisite for ironstone deposition, which may implicate oxidative chemical weathering or suboxic, marine iron cycling. In general, we suggest that the Precambrian record of oolitic ironstones represents an important deep-time archive of iron and nutrient cycling in coastal settings.