Pervasively anoxic surface conditions at the onset of the Great Oxidation Event: New multi-proxy constraints from the Cooper Lake paleosol


Oceanic element inventories derived from marine sedimentary rocks place important constraints on oxidative continental weathering in deep time, but there remains a scarcity in complementary observations directly from continental sedimentary reservoirs. This study focuses on better defining continental weathering conditions near the Archean-Proterozoic boundary through the multi-proxy (major and ultra-trace element, Fe and Cr stable isotopes, µ-XRF elemental mapping, and detrital zircon U-Pb geochronology) investigation of the ca. 2.45 billion year old (giga annum, Ga) Cooper Lake paleosol (saprolith) developed on a sediment-hosted mafic dike within the Huronian Supergroup (Ontario, Canada). Throughout the variably altered Cooper Lake saprolith, ratios of immobile elements (Nb, Ta, Zr, Hf, Th, Al, Ti) are constant, indicating a uniform pre-alteration dike composition, lack of extreme pH weathering conditions, and no major influence from ligand-rich fluids during weathering or burial metasomatism/metamorphism. The loss of Mg, Fe, Na, Sr, and Li, a signature of albite and ferromagnesian silicate weathering, increases towards the top of the preserved profile (unconformity) and dike margins. Coupled bulk rock behaviour of Fe-Mg-Mn and co-localization of Fe-Mn in clay minerals (predominantly chlorite) indicates these elements were solubilized primarily in their divalent state without Fe/Mn-oxide formation. A lack of a Ce anomaly and immobility of Mo, V, and Cr further support pervasively anoxic weathering conditions. Subtle U enrichment, if primary, is the only geochemical evidence that could be consistent with oxidative element mobilization. The leaching of ferromagnesian silicates was accompanied by variable mobility and depletion of transition metals with a relative depletion order of Fe ≈ Mg ≈ Zn > Ni > Co > Cu (Cu being significantly influenced by secondary sulfide formation). Mild enrichment of heavy Fe isotopes (δ 56/54 Fe from 0.169 to 0.492‰) correlating with Fe depletion in the saprolith indicates open-system loss of isotopically light aqueous Fe(II). Minor REE + Y fractionation with increasing alteration intensity, including a decreasing Eu anomaly and Y/Ho ratio, is attributed to albite breakdown and preferential scavenging of HREE > Y by clay minerals, respectively. Younger metasomatism resulted in the addition of several elements (K, Rb, Cs, Be, Tl, Ba, Sn, In, W), partly or wholly obscuring their earlier paleo-weathering trends. The behavior of Cr at Cooper Lake can help test previous hypotheses of an enhanced, low pH-driven continental weathering flux of Cr(III) to marine reservoirs between ca. 2.48–2.32 Ga and the utility of the stable Cr isotope proxy of Mn-oxide induced Cr(III) oxidation. Synchrotron µ-XRF maps and invariant Cr/Nb ratios reveal complete immobility of Cr despite its distribution amongst both clay-rich groundmass and Fe-Ti oxides. Assuming a pH-dependent, continental source of Cr(III) to marine basins, the Cr immobility at Cooper Lake indicates either that signatures of acidic surface waters were localized to uppermost and typically unpreserved regolith horizons or were geographically restricted to acid-generating point sources. However, given detrital pyrite preservation in overlying fluvial sequences, it is probable that the oxidative sulfide corrosion required to drive surface pH 53/52 Cr: −0.321 ± 0.038‰ 2sd, n = 34) that cannot be linked to Cr(III) oxidation and is instead interpreted to have a magmatic origin. The combined paleosol chemical signatures and preservation of detrital pyrite/uraninite indicate low atmospheric O 2 during weathering at ca. 2.45 Ga in the rift-related environment of the Lower Huronian. The aqueous flux from the reduced weathering of mafic rocks was presumably characterized by a greater transition metal (Fe, Mn, Zn, Co, Ni) load with isotopically light Fe(II) compared to modern environments, as well as higher Eu/Eu * and Y/Ho than the source rock. In most models of Precambrian ocean element inventories, hydrothermal fluids are viewed as the main supplier of several metals (e.g., Fe, Zn), although the results herein suggest that a riverine metal supply may have been substantial and that using Eu-excess as a strict proxy for hydrothermal flux may be misleading in near-shore marine sedimentary deposits. </p

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