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Abstract Stratigraphic variability in the geochemistry of sedimentary rocks provides critical data for interpreting paleoenvironmental change throughout Earth history. However, the vast majority of pre-Jurassic geochemical records derive from shallow-water carbonate platforms that may not reflect global ocean chemistry. Here, we used calcium isotope ratios (δ44Ca) in conjunction with minor-element geochemistry (Sr/Ca) and field observations to explore the links among sea-level change, carbonate mineralogy, and marine diagenesis and the expression of a globally documented interval of elevated carbon isotope ratios (δ13C; Hirnantian isotopic carbon excursion [HICE]) associated with glaciation in Upper Ordovician shallow-water carbonate strata from Anticosti Island, Canada, and the Great Basin, Nevada and Utah, USA. The HICE on Anticosti is preserved in limestones with low δ44Ca and high Sr/Ca, consistent with aragonite as a major component of primary mineralogy. Great Basin strata are characterized by lateral gradients in δ44Ca and δ13C that reflect variations in the extent of early marine diagenesis across the platform. In deep-ramp settings, deposition during synglacial sea-level lowstand and subsequent postglacial flooding increased the preservation of an aragonitic signature with elevated δ13C produced in shallow-water environments. In contrast, on the mid- and inner ramp, extensive early marine diagenesis under seawater-buffered conditions muted the magnitude of the shift in δ13C. The processes documented here provide an alternative explanation for variability in a range of geochemical proxies preserved in shallow-water carbonates at other times in Earth history, and challenge the notion that these proxies necessarily record changes in the global ocean.
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Early Mississippian global δ13C excursion is not a diagenetic artifact
Shallow-water platform carbonate δ13C may provide a record of changes in ocean chemistry through time, but early marine diagenesis and local processes can decouple these records from the global carbon cycle. Recent studies of calcium isotopes (δ44/40Ca) in shallow-water carbonates indicate that δ44/40Ca can be altered during early marine diagenesis, implying that δ13C may also potentially be altered. Here, we tested the hypothesis that the platform carbonate δ13C record of the Kinderhookian-Osagean boundary excursion (KOBE), ∼353 m.y. ago, reflects a period of global diagenesis using paired isotopic (δ44/40Ca and clumped isotopes) and trace-element geochemistry from three sections in the United States. There is little evidence for covariation between δ44/40Ca and δ13C during the KOBE. Clumped isotopes from our shallowest section support primarily sediment-buffered diagenesis at relatively low temperatures. We conclude that the δ13C record of the KOBE as recorded in shallow-water carbonate is consistent with a shift in the dissolved inorganic carbon reservoir and that, more generally, ancient shallow-water carbonates can retain records of primary seawater chemistry.
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- PAR ID:
- 10512235
- Publisher / Repository:
- Geological Society of America
- Date Published:
- Journal Name:
- Geology
- ISSN:
- 0091-7613
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1130/G52109.1
