Iron deposition during recovery from Late Devonian oceanic anoxia: Implications of the geochemistry of the Kawame ferromanganese deposit, Nedamo Belt, Northeast Japan

The Late Devonian, during which one of the “Big Five” Phanerozoic mass extinction events occurred, was one of the most important time intervals in Earth history. Nevertheless, the paucity of deep-sea records due to subduction has hampered elucidation of the pelagic environment during the Late Devonian in Panthalassa. However, ancient hydrothermal ferromanganese sediments, which were deposited on the abyssal seafloor and then accreted onto continental margins, are preserved as umber deposits and exposed in accretionary prisms. These sediments can provide key information to characterize the paleo-ocean. An Upper Devonian (Famennian) umber deposit is exposed in Kawame Quarry, Nedamo Belt, northeastern Japan. We investigated the bulk chemical composition and osmium isotopic ratio (¹⁸⁷Os/¹⁸⁸Os) of the Kawame umber to discuss the pelagic environment of the Panthalassa Ocean during the Late Devonian. The Kawame umber shows positive correlations between Fe content and the levels of P, V, Os, and rare earth elements, suggesting that hydrothermal Fe-oxyhydroxide particles adsorbed these elements from ambient seawater in the same way as hydrothermal ferromanganese sediments in the present-day ocean. Newly obtained initial ¹⁸⁷Os/¹⁸⁸Os values of Late Devonian seawater are 0.49–0.57, lower than that of present-day seawater (~1.06) and comparable to Paleogene and Late Cretaceous values. One of the most remarkable characteristics of the Kawame umber is its markedly high Fe levels (up to 90 wt%) compared to present-day seafloor hydrothermal ferromanganese sediments and younger umber deposits in Japanese accretionary complexes. Because seawater ¹⁸⁷Os/¹⁸⁸Os values were not notably different from those during the Paleogene and Late Cretaceous, anomalously vigorous hydrothermal activity in the Late Devonian is unlikely to have caused the increased Fe deposition. The rare earth element patterns of the Kawame umber (normalized to post-Archean average Australian shale) show weaker negative Ce anomalies than those of younger umbers and present-day hydrothermal ferromanganese sediments, suggesting that the Kawame umbers were deposited under less oxidizing conditions. Considering that many red beds were deposited at ~370 Ma, during recovery from the oceanic anoxic events (OAEs) of the Late Devonian (early Famennian), the anomalous Fe enrichment in the Kawame umber likely reflects enhanced oxidization and precipitation of abundant dissolved Fe during the post-OAE transition from anoxic to oxic conditions.