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Published October 23, 2024 | Published
Journal Article Open

Isotopic evidence of acetate turnover in Precambrian continental fracture fluids

  • 1. ROR icon California Institute of Technology
  • 2. ROR icon University of Toronto
  • 3. ROR icon University of Bremen
  • 4. ROR icon University of Ottawa
  • 5. ROR icon The University of Texas System
  • 6. ROR icon Institut de Physique du Globe de Paris

Abstract

The deep continental crust represents a vast potential habitat for microbial life where its activity remains poorly constrained. Organic acids like acetate are common in these ecosystems, but their role in the subsurface carbon cycle - including the mechanism and rate of their turnover - is still unclear. Here, we develop an isotope-exchange 'clock' based on the abiotic equilibration of H-isotopes between acetate and water, which can be used to define the maximum in situ acetate residence time. We apply this technique to the fracture fluids in Birchtree and Kidd Creek mines within the Canadian Precambrian crust. At both sites, we find that acetate residence times are <1 million years and calculated a rate of turnover that could theoretically support microbial life. However, radiolytic water-rock reactions could also contribute to acetate production and degradation, a process that would have global relevance for the deep biosphere. More broadly, our study demonstrates the utility of isotope-exchange clocks in determining residence times of biomolecules with possible applications to other environments.

Copyright and License

© The Author(s) 2024. This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

Acknowledgement

We would like to thank Nathan Dalleska (Caltech) for helpful discussions about sample processing as well as Andreas Hilkert and Dieter Juchelka (Thermo Fisher, Bremen) and the Caltech Proteome Exploration Lab for use of their Orbitrap facilities. Funding for this work came from an NSF Gradaute Research Fellowship DGE-1745301 (to E.P.M.), a European Association of Organic Geochemistry Research Award (to E.P.M.), the NASA Astrobiology Institute grant # 80NSSC18M0094 (to J.M.E. and A.L.S.), a CIFAR Earth 4D grant (to B.S.L. and V.O). This work was also supported by the Deutsche Forschungsgemeinschaft through the Cluster of Excellence “The Ocean Floor – Earth’s Uncharted Interface“ (project 390741603) to V.H.

Contributions

E.P.M. conceptualized and designed the study and performed data analysis. E.P.M., J.P. and M.S. performed sample chemical preparation and Orbitrap analysis. E.P.M., C.H. and V.H. performed isotope exchange reactions. J.B. and A.M. performed DFT calculations. J.E., A.L.S, V.O, B.S.L, K.H., O.W. and W.B. provided laboratory analytical facilities and samples as well as important scientific insights. All authors contributed to data interpretation and manuscript writing.

Data Availability

The data files generated during ESI-Orbitrap analysis of the Kidd Creek and Birchtree fracture fluids is provided in a public GitHub repository (https://doi.org/10.5281/zenodo.13798759)53. Any additional data beyond those found in the repository can be made available on request.

Supplemental Material

Supplementary Information (PDF)

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Additional details

Created:
October 31, 2024
Modified:
October 31, 2024