skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Methane seep carbonates yield clumped isotope signatures out of equilibrium with formation temperatures

Abstract

Here, methane cold seep systems typically exhibit extensive buildups of authigenic carbonate minerals, resulting from local increases in alkalinity driven by methane oxidation. Here, we demonstrate that modern seep authigenic carbonates exhibit anomalously low clumped isotope values (Δ47), as much as ~0.2‰ lower than expected values. In modern seeps, this range of disequilibrium translates into apparent temperatures that are always warmer than ambient temperatures, by up to 50 °C. We examine various mechanisms that may induce disequilibrium behaviour in modern seep carbonates, and suggest that the observed values result from several factors including kinetic isotopic effects during methane oxidation, mixing of inorganic carbon pools, pH effects and rapid precipitation. Ancient seep carbonates studied here also exhibit potential disequilibrium signals. Ultimately, these findings indicate the predominance of disequilibrium clumped isotope behaviour in modern cold seep carbonates that must be considered when characterizing environmental conditions in both modern and ancient cold seep settings.

Authors:
 [1];  [2];  [3];  [4];  [4];  [5];  [6];  [7];  [8];  [9];  [8];  [3]
  1. California State Univ., Fullerton, CA (United States); Univ. of California, Los Angeles, CA (United States)
  2. Northern Arizona Univ., Flagstaff, AZ (United States)
  3. Univ. of California, Los Angeles, CA (United States); Univ. de Brest, Plouzane (France)
  4. Univ. of California, Los Angeles, CA (United States)
  5. Univ. of Bergen, Bergen (Norway)
  6. Oregon State Univ., Corvallis, OR (United States)
  7. California Inst. of Technology (CalTech), Pasadena, CA (United States)
  8. Univ. of California, Riverside, CA (United States)
  9. Univ. of Washington, Seattle, WA (United States)
Publication Date:
Research Org.:
Univ. of California, Los Angeles, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1395567
Grant/Contract Number:  
FG02-13ER16402; SC0010288
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 7; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
58 GEOSCIENCES

Citation Formats

Loyd, S. J., Sample, J., Tripati, R. E., Defliese, W. F., Brooks, K., Hovland, M., Torres, M., Marlow, J., Hancock, L. G., Martin, R., Lyons, T., and Tripati, A. E. Methane seep carbonates yield clumped isotope signatures out of equilibrium with formation temperatures. United States: N. p., 2016. Web. doi:10.1038/ncomms12274.
Loyd, S. J., Sample, J., Tripati, R. E., Defliese, W. F., Brooks, K., Hovland, M., Torres, M., Marlow, J., Hancock, L. G., Martin, R., Lyons, T., & Tripati, A. E. Methane seep carbonates yield clumped isotope signatures out of equilibrium with formation temperatures. United States. doi:10.1038/ncomms12274.
Loyd, S. J., Sample, J., Tripati, R. E., Defliese, W. F., Brooks, K., Hovland, M., Torres, M., Marlow, J., Hancock, L. G., Martin, R., Lyons, T., and Tripati, A. E. Fri . "Methane seep carbonates yield clumped isotope signatures out of equilibrium with formation temperatures". United States. doi:10.1038/ncomms12274. https://www.osti.gov/servlets/purl/1395567.
@article{osti_1395567,
title = {Methane seep carbonates yield clumped isotope signatures out of equilibrium with formation temperatures},
author = {Loyd, S. J. and Sample, J. and Tripati, R. E. and Defliese, W. F. and Brooks, K. and Hovland, M. and Torres, M. and Marlow, J. and Hancock, L. G. and Martin, R. and Lyons, T. and Tripati, A. E.},
abstractNote = {Here, methane cold seep systems typically exhibit extensive buildups of authigenic carbonate minerals, resulting from local increases in alkalinity driven by methane oxidation. Here, we demonstrate that modern seep authigenic carbonates exhibit anomalously low clumped isotope values (Δ47), as much as ~0.2‰ lower than expected values. In modern seeps, this range of disequilibrium translates into apparent temperatures that are always warmer than ambient temperatures, by up to 50 °C. We examine various mechanisms that may induce disequilibrium behaviour in modern seep carbonates, and suggest that the observed values result from several factors including kinetic isotopic effects during methane oxidation, mixing of inorganic carbon pools, pH effects and rapid precipitation. Ancient seep carbonates studied here also exhibit potential disequilibrium signals. Ultimately, these findings indicate the predominance of disequilibrium clumped isotope behaviour in modern cold seep carbonates that must be considered when characterizing environmental conditions in both modern and ancient cold seep settings.},
doi = {10.1038/ncomms12274},
journal = {Nature Communications},
number = ,
volume = 7,
place = {United States},
year = {2016},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 14 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Carbonate clumped isotope bond reordering and geospeedometry
journal, October 2012


Microbial methane oxidation and sulfate reduction at cold seeps of the deep Eastern Mediterranean Sea
journal, June 2009


Biogeochemistry and Community Composition of Iron- and Sulfur-Precipitating Microbial Mats at the Chefren Mud Volcano (Nile Deep Sea Fan, Eastern Mediterranean)
journal, March 2008

  • Omoregie, E. O.; Mastalerz, V.; de Lange, G.
  • Applied and Environmental Microbiology, Vol. 74, Issue 10
  • DOI: 10.1128/AEM.01751-07

Carbonate clumped isotope compositions of modern marine mollusk and brachiopod shells
journal, April 2013

  • Henkes, Gregory A.; Passey, Benjamin H.; Wanamaker, Alan D.
  • Geochimica et Cosmochimica Acta, Vol. 106
  • DOI: 10.1016/j.gca.2012.12.020

U–Th stratigraphy of a cold seep carbonate crust
journal, March 2009


Chemosynthetic bacterial mats at cold hydrocarbon seeps, Gulf of Mexico continental slope
journal, January 1993


18O13C16O in Earth’s atmosphere
journal, December 2004


New perspectives on anaerobic methane oxidation
journal, October 2000


Multiple archaeal groups mediate methane oxidation in anoxic cold seep sediments
journal, May 2002

  • Orphan, V. J.; House, C. H.; Hinrichs, K.-U.
  • Proceedings of the National Academy of Sciences, Vol. 99, Issue 11, p. 7663-7668
  • DOI: 10.1073/pnas.072210299

Evaluation of kinetic effects on clumped isotope fractionation (Δ47) during inorganic calcite precipitation
journal, June 2014


Clumped isotope thermometry of carbonatites as an indicator of diagenetic alteration
journal, July 2010


Complex pockmarks with carbonate-ridges off mid-Norway: Products of sediment degassing
journal, June 2005


Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition
journal, October 2015

  • Tripati, Aradhna K.; Hill, Pamela S.; Eagle, Robert A.
  • Geochimica et Cosmochimica Acta, Vol. 166
  • DOI: 10.1016/j.gca.2015.06.021

Paleo-environmental implication of clumped isotopes in land snail shells
journal, November 2011

  • Zaarur, Shikma; Olack, Gerard; Affek, Hagit P.
  • Geochimica et Cosmochimica Acta, Vol. 75, Issue 22
  • DOI: 10.1016/j.gca.2011.08.044

Methane production and consumption in anoxic marine sediments
journal, January 1976


Methane consumption in Cariaco Trench waters and sediments
journal, January 1976


High-temperature environments of human evolution in East Africa based on bond ordering in paleosol carbonates
journal, June 2010

  • Passey, B. H.; Levin, N. E.; Cerling, T. E.
  • Proceedings of the National Academy of Sciences, Vol. 107, Issue 25
  • DOI: 10.1073/pnas.1001824107

Carbon cycling within the sulfate-methane-transition-zone in marine sediments from the Ulleung Basin
journal, January 2013


13C–18O bonds in carbonate minerals: A new kind of paleothermometer
journal, March 2006

  • Ghosh, Prosenjit; Adkins, Jess; Affek, Hagit
  • Geochimica et Cosmochimica Acta, Vol. 70, Issue 6
  • DOI: 10.1016/j.gca.2005.11.014

Glacial/interglacial temperature variations in Soreq cave speleothems as recorded by ‘clumped isotope’ thermometry
journal, November 2008

  • Affek, Hagit P.; Bar-Matthews, Miryam; Ayalon, Avner
  • Geochimica et Cosmochimica Acta, Vol. 72, Issue 22
  • DOI: 10.1016/j.gca.2008.06.031

The influence of temperature and seawater carbonate saturation state on 13 C– 18 O bond ordering in bivalve mollusks
journal, January 2013


Oregon Subduction Zone: Venting, Fauna, and Carbonates
journal, February 1986


Temperature limits for preservation of primary calcite clumped isotope paleotemperatures
journal, August 2014

  • Henkes, Gregory A.; Passey, Benjamin H.; Grossman, Ethan L.
  • Geochimica et Cosmochimica Acta, Vol. 139
  • DOI: 10.1016/j.gca.2014.04.040

A Methanotrophic Marine Molluscan (Bivalvia, Mytilidae) Symbiosis: Mussels Fueled by Gas
journal, September 1986


13C–18O isotope signatures and ‘clumped isotope’ thermometry in foraminifera and coccoliths
journal, October 2010

  • Tripati, Aradhna K.; Eagle, Robert A.; Thiagarajan, Nivedita
  • Geochimica et Cosmochimica Acta, Vol. 74, Issue 20
  • DOI: 10.1016/j.gca.2010.07.006

Compositional and temperature effects of phosphoric acid fractionation on Δ47 analysis and implications for discrepant calibrations
journal, March 2015


Authigenic carbonates from the Cascadia subduction zone and their relation to gas hydrate stability
journal, January 1998


Isotopic fractionations associated with phosphoric acid digestion of carbonate minerals: Insights from first-principles theoretical modeling and clumped isotope measurements
journal, December 2009

  • Guo, Weifu; Mosenfelder, Jed L.; Goddard, William A.
  • Geochimica et Cosmochimica Acta, Vol. 73, Issue 24
  • DOI: 10.1016/j.gca.2009.05.071

Non-linear mixing effects on mass-47 CO 2 clumped isotope thermometry: Patterns and implications : Non-linear mixing effects on mass-47 clumped isotopes
journal, March 2015

  • Defliese, William F.; Lohmann, Kyger C.
  • Rapid Communications in Mass Spectrometry, Vol. 29, Issue 9
  • DOI: 10.1002/rcm.7175

Effect of hydrostatic pressure and salinity on the stability of gas hydrates
journal, March 1990


Surface kinetic model for isotopic and trace element fractionation during precipitation of calcite from aqueous solutions
journal, February 2011


Eocene bipolar glaciation associated with global carbon cycle changes
journal, July 2005

  • Tripati, Aradhna; Backman, Jan; Elderfield, Henry
  • Nature, Vol. 436, Issue 7049
  • DOI: 10.1038/nature03874

Deep-Sea Archaea Fix and Share Nitrogen in Methane-Consuming Microbial Consortia
journal, October 2009


Water column methane oxidation adjacent to an area of active hydrate dissociation, Eel river Basin
journal, August 2001

  • Valentine, David L.; Blanton, Douglas C.; Reeburgh, William S.
  • Geochimica et Cosmochimica Acta, Vol. 65, Issue 16
  • DOI: 10.1016/S0016-7037(01)00625-1

Carbonate clumped isotope thermometry of deep-sea corals and implications for vital effects
journal, August 2011

  • Thiagarajan, Nivedita; Adkins, Jess; Eiler, John
  • Geochimica et Cosmochimica Acta, Vol. 75, Issue 16
  • DOI: 10.1016/j.gca.2011.05.004

Defining an absolute reference frame for ‘clumped’ isotope studies of CO2
journal, November 2011

  • Dennis, Kate J.; Affek, Hagit P.; Passey, Benjamin H.
  • Geochimica et Cosmochimica Acta, Vol. 75, Issue 22
  • DOI: 10.1016/j.gca.2011.09.025