Dual carbonate clumped isotope (Δ47-Δ48) measurements constrain different sources of kinetic isotope effects and quasi-equilibrium signatures in cave carbonates
Abstract
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 ΔΔi 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.
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- 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
- OSTI Identifier:
- 2222507
- Alternate Identifier(s):
- OSTI ID: 2338081
- Grant/Contract Number:
- FG02-83613ER16402; AC02-05CH11231; 2022-3314; 386188-2010; 2015-04413; 2020-05810; 2002509; 1405472; 1603056; 1806090; 2103129
- Resource Type:
- Published Article
- Journal Name:
- Geochimica et Cosmochimica Acta
- Additional Journal Information:
- Journal Name: Geochimica et Cosmochimica Acta Journal Volume: 366 Journal Issue: C; Journal ID: ISSN 0016-7037
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 58 GEOSCIENCES; speleothems; clumped isotopes; cave carbonates
Citation Formats
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., and Tripati, Aradhna. Dual carbonate clumped isotope (Δ47-Δ48) measurements constrain different sources of kinetic isotope effects and quasi-equilibrium signatures in cave carbonates. United States: N. p., 2024.
Web. doi:10.1016/j.gca.2023.11.017.
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. Dual carbonate clumped isotope (Δ47-Δ48) measurements constrain different sources of kinetic isotope effects and quasi-equilibrium signatures in cave carbonates. United States. https://doi.org/10.1016/j.gca.2023.11.017
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., and Tripati, Aradhna. Thu .
"Dual carbonate clumped isotope (Δ47-Δ48) measurements constrain different sources of kinetic isotope effects and quasi-equilibrium signatures in cave carbonates". United States. https://doi.org/10.1016/j.gca.2023.11.017.
@article{osti_2222507,
title = {Dual carbonate clumped isotope (Δ47-Δ48) measurements constrain different sources of kinetic isotope effects and quasi-equilibrium signatures in cave carbonates},
author = {Parvez, Zeeshan A. and El-Shenawy, Mohammed I. and Lucarelli, Jamie K. and Kim, Sang-Tae and Johnson, Kathleen R. and Wright, Kevin and Gebregiorgis, Daniel and Montanez, Isabel P. and Wortham, Barbara and Asrat, Asfawossen and Reinhardt, Eduard and Christensen, John N. and Matamoros, Irvin W. and Rubi, Joshua and Miguel, Kevin and Elliott, Ben M. and Flores, Randy and Kovacs, Shawn and Eagle, Robert A. and Tripati, Aradhna},
abstractNote = {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 ΔΔi 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.},
doi = {10.1016/j.gca.2023.11.017},
journal = {Geochimica et Cosmochimica Acta},
number = C,
volume = 366,
place = {United States},
year = {Thu Feb 01 00:00:00 EST 2024},
month = {Thu Feb 01 00:00:00 EST 2024}
}
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