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• W3018571947 endingPage "184" @default.
• W3018571947 startingPage "161" @default.
• W3018571947 abstract "Despite iron and trace element proxies informing much of our insight into Earth’s oxygenation history, the processes that controlled their accumulation and distribution in ancient sedimentary environments are not fully understood. Furthermore, deciphering between primary, depositional signals and oxidative weathering alteration poses a substantial challenge to reconstructing Earth’s redox history using its sedimentary record. Here, we present a multi-proxy geochemical investigation of three transgressive shale intervals from the ca. 811 Ma Reefal assemblage (upper Fifteenmile Group) in Yukon, Canada to help resolve these issues. Systematic stratigraphic trends from low to high FeHR/FeT and FeT/Al compositions across shale intervals represent shoaling of a discrete redoxcline that separated oxygenated surface waters from anoxic, ferruginous deep waters during marine transgression. In some cases, these trends are followed by a symmetric fall, which represents a full “transgressive-regressive cycle” of the redoxcline. The high proportion of glauconite to total illite indicate short-term oscillating redox conditions as the redoxcline migrated across the sediment-water interface during relative sea-level rise. These conditions invigorated dissimilatory iron reduction (DIR) within anoxic sediment pore waters, which released Fe(II) into the overlying water column where it was oxidized to iron oxy(hydr)oxide and shuttled downslope. High rates of DIR within sediment replete with highly reactive iron oxy(hydr)oxide and organic matter removed isotopically light, bio-available iron, rendering the residual sediment depleted in FeT/Al relative to the detrital baseline and enriched in 56Fe. The low iron content of the detrital flux to the basin (Fe/Al ∼ 0.3) rendered the sediment susceptible to changes in its bulk δ56Fe composition by modification of its authigenic components alone and enabled fractionation from DIR to drive bulk-rock δ56Fe values up to 0.8‰. Anomalously high concentrations of redox-sensitive elements in three samples (up to 5792 ppm Cr, 586 ppm Mn, 726 ppm Mo, and 3509 ppm Ni) and their relative distribution patterns show similarities to co-enrichment due to particulate shuttling within a weakly restricted basin. However, SEM-EDS element maps and large-area BSE image mosaics show the remains of framboidal pyrite “ghosts” with secondary enrichment of redox-sensitive elements. Thus, these geochemical trends in redox-sensitive trace metals most likely reflect mobilization and re-accumulation following pyrite dissolution during outcrop weathering. The low primary pyrite content and local transformation of pyrite iron to iron oxy(hdr)oxide suggest that δ56Fe and FeHR/FeT data were unaltered despite indications of pyrite weathering. Ultimately, this dataset elucidates key aspects of sedimentary redox cycling directly preceding evolutionary milestones and a major perturbation to the global carbon cycle and also provides a template for evaluating the effects of outcrop weathering on commonly used sedimentary redox proxies." @default.
• W3018571947 created "2020-05-01" @default.
• W3018571947 creator A5004525663 @default.
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• W3018571947 creator A5082041080 @default.
• W3018571947 date "2020-07-01" @default.
• W3018571947 modified "2023-10-16" @default.
• W3018571947 title "Geochemical signatures of transgressive shale intervals from the 811 Ma Fifteenmile Group in Yukon, Canada: Disentangling sedimentary redox cycling from weathering alteration" @default.
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