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Abstract Organic and inorganic stable isotopes of lacustrine carbonate sediments are commonly used in reconstructions of ancient terrestrial ecosystems and environments. Microbial activity and local hydrological inputs can alter porewater chemistry (e.g., pH, alkalinity) and isotopic composition (e.g., δ18Owater, δ13CDIC), which in turn has the potential to impact the stable isotopic compositions recorded and preserved in lithified carbonate. The fingerprint these syngenetic processes have on lacustrine carbonate facies is yet unknown, however, and thus, reconstructions based on stable isotopes may misinterpret diagenetic records as broader climate signals. Here, we characterize geochemical and stable isotopic variability of carbonate minerals, organic matter, and water within one modern lake that has known microbial influences (e.g., microbial mats and microbialite carbonate) and combine these data with the context provided by 16S rRNA amplicon sequencing community profiles. Specifically, we measure oxygen, carbon, and clumped isotopic compositions of carbonate sediments (δ18Ocarb, δ13Ccarb, ∆47), as well as carbon isotopic compositions of bulk organic matter (δ13Corg) and dissolved inorganic carbon (DIC; δ13CDIC) of lake and porewater in Great Salt Lake, Utah from five sites and three seasons. We find that facies equivalent to ooid grainstones provide time‐averaged records of lake chemistry that reflect minimal alteration by microbial activity, whereas microbialite, intraclasts, and carbonate mud show greater alteration by local microbial influence and hydrology. Further, we find at least one occurrence of ∆47isotopic disequilibrium likely driven by local microbial metabolism during authigenic carbonate precipitation. The remainder of the carbonate materials (primarily ooids, grain coatings, mud, and intraclasts) yield clumped isotope temperatures (T(∆47)), δ18Ocarb, and calculated δ18Owaterin isotopic equilibrium with ambient water and temperature at the time and site of carbonate precipitation. Our findings suggest that it is possible and necessary to leverage diverse carbonate facies across one sedimentary horizon to reconstruct regional hydroclimate and evaporation–precipitation balance, as well as identify microbially mediated carbonate formation.
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A Combined Model for Kinetic Clumped Isotope Effects in the CaCO 3 ‐DIC‐H 2 O System
Abstract Most Earth surface carbonates precipitate out of isotopic equilibrium with their host solution, complicating the use of stable isotopes in paleoenvironment reconstructions. Disequilibrium can arise from exchange reactions in the DIC‐H2O system as well as during crystal growth reactions in the DIC‐CaCO3system. Existing models account for kinetic isotope effects (KIEs) in these systems separately but the models have yet to be combined in a general framework. Here, an open‐system box model is developed for describing disequilibrium carbon, oxygen, and clumped (Δ47, Δ48, and Δ49) isotope effects in the CaCO3‐DIC‐H2O system. The model is used to simulate calcite precipitation experiments in which the fluxes and isotopic compositions of CO2and CaCO3were constrained. Using a literature compilation of equilibrium and kinetic fractionation factors, modeledδ18O and Δ47values of calcite are in good agreement with the experimental data covering a wide range in crystal growth rate and solution pH. This relatively straightforward example provides a foundation for adapting the model to other situations involving CO2absorption (e.g., corals, foraminifera, and high‐pH travertines) or degassing (e.g., speleothems, low‐pH travertines, and cryogenic carbonates) and/or mixing with other dissolved inorganic carbon sources.
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- Award ID(s):
- 1749183
- PAR ID:
- 10373126
- Publisher / Repository:
- DOI PREFIX: 10.1029
- Date Published:
- Journal Name:
- Geochemistry, Geophysics, Geosystems
- Volume:
- 23
- Issue:
- 8
- ISSN:
- 1525-2027
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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