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

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

Journal Article · Thu Feb 01 00:00:00 EST 2024 · Geochimica et Cosmochimica Acta

DOI:https://doi.org/10.1016/j.gca.2023.11.017· OSTI ID:2222507

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.;

Cave carbonate minerals are an important terrestrial paleoclimate archive. A few studies have explored the potential for applying carbonate clumped isotope thermometry to speleothems as a tool for constraining past temperatures. To date, most papers utilizing this method have focused on mass-47 clumped isotope values (Δ₄₇) at a single location and reported that cave carbonate minerals rarely achieve isotopic equilibrium, with kinetic isotope effects (KIEs) attributed to CO₂ degassing. More recently, studies have shown that mass-47 and mass-48 CO₂ from acid digested carbonate minerals (Δ₄₇ and Δ₄₈) can be used together to assess equilibrium and probe KIEs. Here, we examined 44 natural and synthetic modern cave carbonate mineral samples from 13 localities with varying environmental conditions (ventilation, water level, pCO₂, temperature) for (dis)equilibrium using Δ₄₇-Δ₄₈ values, in concert with traditional stable carbon (δ¹³C) and oxygen (δ¹⁸O) isotope ratios. Data showed that 19 of 44 samples exhibited Δ₄₇-Δ₄₈ values indistinguishable from isotopic equilibrium, and 18 (95 %) of these samples yield Δ₄₇-predicted temperatures within error of measured modern temperatures. Conversely, 25 samples exhibited isotopic disequilibria, 13 of which yield erroneous temperature estimates. Within some speleothem samples, we find Δ₄₇-Δ₄₈ values consistent with CO₂ degassing effects, however, the majority of samples with KIEs are consistent with other processes being dominant. We hypothesize that these values reflect isotopic buffering effects on clumped isotopes that can be considerable and cannot be overlooked. Using a Raleigh Distillation Model, we examined carbon and oxygen isotope exchange trajectories and their relationships with dual clumped isotope disequilibria. Carbon isotope exchange is associated with depletion of both Δ₄₇ and Δ₄₈ relative to equilibrium, while oxygen isotope exchange is associated with enrichment of both Δ₄₇ and Δ₄₈ relative to equilibrium. Cave rafts collected from proximate locations in Mexico exhibit the largest average departures from equilibrium ($$Δ\bar{Δ}$$₄₇ = -0.032 ± 0.007, $$Δ\bar{Δ}$$₄₈ = -0.104 ± 0.035, where ΔΔ_i is the measured value – the equilibrium value). This study shows how the Δ₄₇-Δ₄₈ dual carbonate clumped isotope framework can be applied to a variety of tcave carbonate mineral samples, enabling identification of isotopic equilibria and therefore quantitative application of clumped isotope thermometry for paleoclimate reconstruction, or alternatively, constraining the mechanisms of kinetic effects.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Heising-Simons Foundation; Natural Science and Engineering Research Council (NSERC); National Science Foundation (NSF); Packard Foundation; Sloan Foundation; Silicon Valley Community Foundation

Grant/Contract Number:: FG02-83613ER16402; AC02-05CH11231; 2022-3314; 386188-2010; 2015-04413; 2020-05810; 2002509; 1405472; 1603056; 1806090; 2103129

OSTI ID:: 2222507

Alternate ID(s):: OSTI ID: 2338081

Journal Information:: Geochimica et Cosmochimica Acta, Journal Name: Geochimica et Cosmochimica Acta Vol. 366 Journal Issue: C; ISSN 0016-7037

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Quantifying kinetic fractionation in Bunker Cave speleothems using Δ47 Kluge, Tobias; Affek, Hagit P. Quaternary Science Reviews, Vol. 49 https://doi.org/10.1016/j.quascirev.2012.06.013	journal	August 2012
The Cave Environment Poulson, Thomas L.; White, William B. Science, Vol. 165, Issue 3897 https://doi.org/10.1126/science.165.3897.971	journal	September 1969
Carbonate clumped isotope analysis (Δ ₄₇ ) of 21 carbonate standards determined via gas‐source isotope‐ratio mass spectrometry on four instrumental configurations using carbonate‐based standardization and multiyear data sets Upadhyay, Deepshikha; Lucarelli, Jamie; Arnold, Alexandrea Rapid Communications in Mass Spectrometry, Vol. 35, Issue 17 https://doi.org/10.1002/rcm.9143	journal	July 2021
A Combined Model for Kinetic Clumped Isotope Effects in the CaCO₃‐DIC‐H₂O System Watkins, James M.; Devriendt, Laurent S. Geochemistry, Geophysics, Geosystems, Vol. 23, Issue 8 https://doi.org/10.1029/2021GC010200	journal	August 2022
Defining an absolute reference frame for ‘clumped’ isotope studies of CO2 Dennis, Kate J.; Affek, Hagit P.; Passey, Benjamin H. Geochimica et Cosmochimica Acta, Vol. 75, Issue 22 https://doi.org/10.1016/j.gca.2011.09.025	journal	November 2011
Equilibrium and nonequilibrium oxygen isotope effects in synthetic carbonates Kim, Sang-Tae; O'Neil, James R. Geochimica et Cosmochimica Acta, Vol. 61, Issue 16 https://doi.org/10.1016/S0016-7037(97)00169-5	journal	August 1997

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

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