Dual carbonate clumped isotope (Δ47-Δ48) measurements constrain different sources of kinetic isotope effects and quasi-equilibrium signatures in cave carbonates

Parvez, Zeeshan A.; El-Shenawy, Mohammed I.; Lucarelli, Jamie K.; Kim, Sang-Tae; Johnson, Kathleen R.; Wright, Kevin; Gebregiorgis, Daniel; Montanez, Isabel P.; Wortham, Barbara; Asrat, Asfawossen; Reinhardt, Eduard; Christensen, John N.; Matamoros, Irvin W.; Rubi, Joshua; Miguel, Kevin; Elliott, Ben M.; Flores, Randy; Kovacs, Shawn; Eagle, Robert A.; Tripati, Aradhna

doi:10.1016/j.gca.2023.11.017

Cited by 3 publications

(2 citation statements)

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“…Lake carbonates that form rapidly as a result of supersaturation of calcium carbonate can preserve δ 18 O and ∆ 47 values that are out of equilibrium with their formation temperature (e.g., Ingalls, Blättler, et al., 2020; Ingalls, Frantz, et al., 2020; Leng & Marshall, 2004). Paired analyses of ∆ 47 and ∆ 48 can fingerprint clumped isotope disequilibrium and constrain the driving mechanism without knowing the temperature or isotopic composition of ancient lake water (e.g., Bajnai et al., 2020, 2021; Davies et al., 2022; Fiebig et al., 2019; Lu & Swart, 2023; Parvez et al., 2024; Staudigel, Davies, et al., 2023; Staudigel, Pederson, et al., 2023; Tagliavento et al., 2023). Specifically, removal of CO 2 from the carbonate system (“degassing” in Bajnai et al.…”

Section: Introductionmentioning

confidence: 99%

“…Lake carbonates that form rapidly as a result of supersaturation of calcium carbonate can preserve δ 18 O and ∆ 47 values that are out of equilibrium with their formation temperature (e.g., Ingalls, Blättler, et al, 2020;Ingalls, Frantz, et al, 2020;Leng & Marshall, 2004). Paired analyses of ∆ 47 and ∆ 48 can fingerprint clumped isotope disequilibrium and constrain the driving mechanism without knowing the temperature or isotopic composition of ancient lake water (e.g., Bajnai et al, 2020Bajnai et al, , 2021Davies et al, 2022;Fiebig et al, 2019;Lu & Swart, 2023;Parvez et al, 2024;Staudigel, Pederson, et al, 2023;Tagliavento et al, 2023). Specifically, removal of CO 2 from the carbonate system ("degassing" in Bajnai et al (2020)) tends to generate lower ∆ 47 and higher ∆ 48 values than the line of mutual equilibrium during the re-equilibration process, whereas addition of new CO 2 from an external pool produces positive ∆ 47 and/or negative ∆ 48 offsets from equilibrium (W. Guo, 2020;Tripati et al, 2015;Uchikawa et al, 2021;Watkins & Devriendt, 2022; Figure 1).…”

Section: Introductionmentioning

confidence: 99%

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Microbial Autotrophy Recorded by Carbonate Dual Clumped Isotope Disequilibrium

Ingalls,

Leapaldt,

Lloyd

2024

Geochem Geophys Geosyst

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The proliferation of microbial carbon fixation is a key control on the evolution of the biosphere and global carbon cycle. Most records of these metabolisms in ancient rocks come from organic matter or fossils, which are not always preserved. Here, we present a potential proxy for microbial carbon fixation (autotrophy) based on the isotopic composition of carbonate minerals. Autotrophs influence carbonate chemistry in the cellular microenvironment by decreasing CO2 concentration and increasing the carbonate saturation state. This can induce rapid precipitation of carbonate minerals that are out of isotopic equilibrium with their environment. Recent work has identified disequilibrated dual clumped isotope compositions (∆47 and ∆48) in the skeletal fossils of marine calcifying organisms. Here we test whether the same is true of non‐skeletal carbonate fabrics associated with microbial autotrophs in modern and Eocene lakes. We found that microbial carbonate formed via autotrophic metabolism recorded lower ∆47 and higher ∆48 values (−∆47/+∆48) than predicted for thermodynamic equilibrium mineral formation. Our findings are supported by models of dual clumped isotope kinetics in the DIC system, and disequilibrium in the oxygen isotope system. We hypothesize that the inverse trajectory away from the equilibrium line (+∆47/−∆48) should be recorded by carbonates formed in association with alkalinizing heterotrophs, such as sulfate reducers. If so, carbonate dual clumped isotopes could be a powerful tool to identify the proliferation and rate of heterotrophic and autotrophic metabolisms in the carbonate rock record on Earth and (perhaps) other planets.

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Section: Introductionmentioning

confidence: 99%

“…Lake carbonates that form rapidly as a result of supersaturation of calcium carbonate can preserve δ 18 O and ∆ 47 values that are out of equilibrium with their formation temperature (e.g., Ingalls, Blättler, et al, 2020;Ingalls, Frantz, et al, 2020;Leng & Marshall, 2004). Paired analyses of ∆ 47 and ∆ 48 can fingerprint clumped isotope disequilibrium and constrain the driving mechanism without knowing the temperature or isotopic composition of ancient lake water (e.g., Bajnai et al, 2020Bajnai et al, , 2021Davies et al, 2022;Fiebig et al, 2019;Lu & Swart, 2023;Parvez et al, 2024;Staudigel, Pederson, et al, 2023;Tagliavento et al, 2023). Specifically, removal of CO 2 from the carbonate system ("degassing" in Bajnai et al (2020)) tends to generate lower ∆ 47 and higher ∆ 48 values than the line of mutual equilibrium during the re-equilibration process, whereas addition of new CO 2 from an external pool produces positive ∆ 47 and/or negative ∆ 48 offsets from equilibrium (W. Guo, 2020;Tripati et al, 2015;Uchikawa et al, 2021;Watkins & Devriendt, 2022; Figure 1).…”

Section: Introductionmentioning

confidence: 99%

Microbial Autotrophy Recorded by Carbonate Dual Clumped Isotope Disequilibrium

Ingalls,

Leapaldt,

Lloyd

2024

Geochem Geophys Geosyst

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Late-stage evolution of hypogene caves at Tyuya-Muyun (Kyrgyzstan): Quantitative insights from mineral deposits

Koltai,

Spötl,

Rinyu

et al. 2024

Chemical Geology

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Recent Efforts to Improve the Accuracy and Precision of Carbonate Clumped‐Isotope Analysis

Oikawa,

Abe,

Iryu

2024

Island Arc

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The carbonate clumped‐isotope thermometer, a relatively recent innovation, is based on the strong relationship between 13C‐18O bond abundance in carbonates and their formation temperature. It can measure temperatures solely based on the CO2 extracted from carbonates and has attracted attention as it accurately reconstructs surface water temperatures on a geological timescale. However, at the time of development, there were many limitations in its application to paleoenvironmental reconstruction such as the large sample size (10 mg), the complicated organic contaminant removal process, and the lack of internationally recognized carbonate standards, and improvements in the measurement method were required. Here, we review the studies conducted since the thermometer development to improve the accuracy and precision of carbonate clumped‐isotope analysis. Finally, we discuss advanced carbonate clumped‐isotope analysis methods, including laser spectroscopy.

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Dual carbonate clumped isotope (Δ47-Δ48) measurements constrain different sources of kinetic isotope effects and quasi-equilibrium signatures in cave carbonates

Cited by 3 publications

References 91 publications

Microbial Autotrophy Recorded by Carbonate Dual Clumped Isotope Disequilibrium

Microbial Autotrophy Recorded by Carbonate Dual Clumped Isotope Disequilibrium

Late-stage evolution of hypogene caves at Tyuya-Muyun (Kyrgyzstan): Quantitative insights from mineral deposits

Recent Efforts to Improve the Accuracy and Precision of Carbonate Clumped‐Isotope Analysis

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