Iron Isotopes Reveal A Benthic Iron Shuttle In The Palaeoproterozoic Zaonega Formation: Basinal Restriction, Euxinia, And The Effect On Global Palaeoredox Proxies

The Zaonega Formation in northwest Russia (similar to 2.0 billion years old) is amongst the most complete successions that record the middle of the Palaeoproterozoic era. As such, geochemical data from the formation have played a central role in framing the debate over redox dynamics in the aftermath of the Great Oxidation Event (GOE). However, uncertainty over local redox conditions and the degree of hydrographic restriction in the formation has led to contradictory interpretations regarding global oxygen (O-2) fugacity. Here, we provide new iron (Fe) isotope data together with major and trace element concentrations to constrain the local physiochemical conditions. The Zaonega Formation sediments show authigenic Fe accumulation (Fe/Al >> 1 wt.%/wt.%) and delta Fe-56 ranging from -0.58 parts per thousand to +0.60 parts per thousand. Many of the data fall on a negative Fe/Al versus delta Fe-56 trend, diagnostic of a benthic Fe shuttle, which implies that Zaonega Formation rocks formed in a redox-stratified and semi-restricted basin. However, basin restriction did not coincide with diminished trace metal enrichment, likely due to episodes of deep-water exchange with metal-rich oxygenated seawater, as evidenced by simultaneous authigenic Fe(III) precipitation. If so, the Onega Basin maintained a connection that allowed its sediments to record signals of global ocean chemistry despite significant basinal effects.