TY - JOUR

T1 - Marine diagenesis of ikaite

T2 - Implications from the isotopic and geochemical composition of glendonites and host concretions (Palaeogene–Neogene sediments, Sakhalin Island)

AU - Vasileva, Kseniia

AU - Vereshchagin, Oleg

AU - Ershova, Victoria

AU - Rogov, Mikhail

AU - Chernyshova, Irina

AU - Vishnevskaya, Irina

AU - Okuneva, Tatiana

AU - Pokrovsky, Boris

AU - Tuchkova, Marianna

AU - Saphronova, Natalia

AU - Kostrov, Yuri

AU - Khmarin, Eduard

N1 - Funding Information: The work was carried out using the analytical capabilities of the Resource Centers of St. Petersburg State University ‘X‐ray Diffraction Centre’, ‘Microscopy and microanalysis’, and ‘Geomodel’. The study is supported by RFBR, project number 20‐35‐70012. Authors are very grateful to Dr Petr Fedorov (Saint Petersburg State University) and Dr Tatsuya Hayashi (Kyushu University) for identifying the diatom shells. Special thanks to James Barnet (Camborne School of Mines) for editing the English. We greatly appreciate careful edits and useful suggestions from our anonymous reviewers, Editor in Chief, Dr Peir Pufahl and Associate Editor, Dr Alexander Brasier. Publisher Copyright: © 2021 The Authors. Sedimentology © 2021 International Association of Sedimentologists Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/8

Y1 - 2021/8

N2 - Glendonites represent pseudomorphs after calcium carbonate hexahydrate (ikaite) and can be used as indicators of past cold climates, because ikaite only naturally occurs in cold environments (<7°C) in the modern. The results of a multi-proxy study of 11 glendonite and host concretion samples from Palaeogene (Gennoishi Formation) and Neogene (Bora and Vengeri formations) sediments from Sakhalin Island, Russian Far East are reported here. Petrographic, cathodoluminescence, powder X-ray diffraction and scanning electron microscope analyses reveal that glendonites are composed of several successive mineralogical phases: low-magnesium ikaite-derived calcite, high-magnesium acicular cement (calcite and dolomite) and blocky calcite or authigenic quartz filling the remaining pore space. Host concretions comprise sandy limestones cemented by high-magnesium calcite. The δ13C and δ18O values for host concretions and enclosed glendonites are very similar, with δ13C ranging from –20.3 to +1.9‰ Vienna Pee-Dee Belemnite and δ18O ranging from –3.4 to +3.4‰ Vienna Pee-Dee Belemnite. Such isotopic values suggest that seawater was the main source of oxygen, while dissolved inorganic carbon and decaying organic matter were the main carbon sources for ikaite growth, concretion and glendonite cementation. The 87Sr/86Sr values within the glendonites and host concretions are significantly lower compared with coeval Palaeogene–Neogene marine carbonates, suggesting an influence of continental runoff on their isotopic composition. Post Archean Australian Shale normalized rare earth element patterns display negative Ce anomalies and positive Eu anomalies, with a depletion in light rare earth elements or bulge in middle rare earth elements. Such spectra of rare earth elements indicate that ikaite growth and replacement occurred very close to the aerobic–anaerobic boundary, with pore waters derived from trapped seawater and/or ikaite dehydration. Since Mg/Ca ratios and alkalinity increase with depth below the sediment–water interface, subsequent mineral phases show enrichment in Mg, while the lack of diagenetic alteration by basinal fluids enabled preservation of the primary isotopic and geochemical characteristics of ikaite within the recrystallized pseudomorph.

AB - Glendonites represent pseudomorphs after calcium carbonate hexahydrate (ikaite) and can be used as indicators of past cold climates, because ikaite only naturally occurs in cold environments (<7°C) in the modern. The results of a multi-proxy study of 11 glendonite and host concretion samples from Palaeogene (Gennoishi Formation) and Neogene (Bora and Vengeri formations) sediments from Sakhalin Island, Russian Far East are reported here. Petrographic, cathodoluminescence, powder X-ray diffraction and scanning electron microscope analyses reveal that glendonites are composed of several successive mineralogical phases: low-magnesium ikaite-derived calcite, high-magnesium acicular cement (calcite and dolomite) and blocky calcite or authigenic quartz filling the remaining pore space. Host concretions comprise sandy limestones cemented by high-magnesium calcite. The δ13C and δ18O values for host concretions and enclosed glendonites are very similar, with δ13C ranging from –20.3 to +1.9‰ Vienna Pee-Dee Belemnite and δ18O ranging from –3.4 to +3.4‰ Vienna Pee-Dee Belemnite. Such isotopic values suggest that seawater was the main source of oxygen, while dissolved inorganic carbon and decaying organic matter were the main carbon sources for ikaite growth, concretion and glendonite cementation. The 87Sr/86Sr values within the glendonites and host concretions are significantly lower compared with coeval Palaeogene–Neogene marine carbonates, suggesting an influence of continental runoff on their isotopic composition. Post Archean Australian Shale normalized rare earth element patterns display negative Ce anomalies and positive Eu anomalies, with a depletion in light rare earth elements or bulge in middle rare earth elements. Such spectra of rare earth elements indicate that ikaite growth and replacement occurred very close to the aerobic–anaerobic boundary, with pore waters derived from trapped seawater and/or ikaite dehydration. Since Mg/Ca ratios and alkalinity increase with depth below the sediment–water interface, subsequent mineral phases show enrichment in Mg, while the lack of diagenetic alteration by basinal fluids enabled preservation of the primary isotopic and geochemical characteristics of ikaite within the recrystallized pseudomorph.

KW - Early diagenesis

KW - ikaite–glendonite transformation

KW - rare earth element

KW - Sr isotopic system

KW - stable isotopes

UR - http://www.scopus.com/inward/record.url?scp=85102697716&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/ab3c45a6-d82c-331d-b00a-4d117ec25708/

U2 - 10.1111/sed.12847

DO - 10.1111/sed.12847

M3 - Article

AN - SCOPUS:85102697716

VL - 68

SP - 2227

EP - 2251

JO - Sedimentology

JF - Sedimentology

SN - 0037-0746

IS - 5

ER -