Experimental calibration of clumped isotopes in siderite between 8.5 and 62 °C and its application as paleo-thermometer in paleosols

Joep van Dijk; Alvaro Fernandez; Julian C. Storck; Timothy S. White; Mark Lever; Inigo A. Müller; Stewart Bishop; Reto F. Seifert; Steven G. Driese; Alexey Krylov; Gregory A. Ludvigson; Alexandra V. Turchyn; Chin Yik Lin; Chad Wittkop; Stefano M. Bernasconi

doi:10.1016/j.gca.2019.03.018

Experimental calibration of clumped isotopes in siderite between 8.5 and 62 °C and its application as paleo-thermometer in paleosols

Joep van Dijk, Alvaro Fernandez, Julian C. Storck, Timothy S. White, Mark Lever, Inigo A. Müller, Stewart Bishop, Reto F. Seifert, Steven G. Driese, Alexey Krylov, Gregory A. Ludvigson, Alexandra V. Turchyn, Chin Yik Lin, Chad Wittkop, Stefano M. Bernasconi

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

The clumped isotope composition of carbonates can be directly related to their formation temperature in the environment, but a robust temperature calibration for siderite is still lacking, and thus limits the applicability of this tool. Here, we present a new calibration for the clumped isotope composition of siderites precipitated with two different techniques between 8.5 and 62 °C: Δ ₄₇ =0.0428±0.002∗[Formula presented]+0.0683±0.022±95%CL,TinKelvinR ² =0.92 The slope of our calibration obtained at an acid digestion temperature of 115 °C is statistically indistinguishable from recently published calcite and dolomite clumped isotope calibrations. The intercept differs from calcite at phosphoric acid digestion temperatures of 70 and 115 °C due to a difference in phosphoric acid fractionation, highlighting the necessity of a siderite specific calibration. We performed the first survey of the clumped isotope compositions of siderites from different environmental settings at ambient temperatures including two permanently waterlogged swamp sites as modern analogues for pedogenic siderite formation in the geologic record. We conclude that pedogenic siderites form at temperatures between the Mean Annual Air Temperature (MAAT) and the summer air temperature highlighting the strong potential of siderites for paleoclimate reconstructions in continental environments.

Original language	English
Pages (from-to)	1-20
Number of pages	20
Journal	Geochimica et Cosmochimica Acta
Volume	254
DOIs	https://doi.org/10.1016/j.gca.2019.03.018
Publication status	Published - 1 Jun 2019
Externally published	Yes

Funding

We thank Madalina Jaggi and Felix Marxer for assistance in the laboratory and Dani Or for help with the soil temperature modelling. JD and SB acknowledge financial support through ETH project ETH-3314-1 and SNF projects 200020_160046 and 200021_169849. SGD and GAL gratefully acknowledge financial support through grant NSF EAR064334 . AK acknowledges support from the Russian Foundation for Basic Research (RFBR) grant RFBR-16-05-00979 . CW acknowledges support from the US National Science Foundation (NSF) grant NSF-1462297 and the National Lacustrine Core Facility (LacCore), Department of Earth Sciences, University of Minnesota-Twin Cities for storing the Otter Lake sample. Field work in the Norfolk Salt Marsh was funded through an ERC StG to AVT 3075842 CARBONSINK. All raw data can be received from SB upon request. We thank Jens Fiebig and three anonymous reviewers for providing constructive feedback that significantly improved the manuscript. Appendix A

Keywords

Clumped isotope thermometry
Paleosols
Siderite

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10.1016/j.gca.2019.03.018

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van Dijk, J., Fernandez, A., Storck, J. C., White, T. S., Lever, M., Müller, I. A., Bishop, S., Seifert, R. F., Driese, S. G., Krylov, A., Ludvigson, G. A., Turchyn, A. V., Lin, C. Y., Wittkop, C., & Bernasconi, S. M. (2019). Experimental calibration of clumped isotopes in siderite between 8.5 and 62 °C and its application as paleo-thermometer in paleosols. Geochimica et Cosmochimica Acta, 254, 1-20. https://doi.org/10.1016/j.gca.2019.03.018

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title = "Experimental calibration of clumped isotopes in siderite between 8.5 and 62 °C and its application as paleo-thermometer in paleosols",

abstract = " The clumped isotope composition of carbonates can be directly related to their formation temperature in the environment, but a robust temperature calibration for siderite is still lacking, and thus limits the applicability of this tool. Here, we present a new calibration for the clumped isotope composition of siderites precipitated with two different techniques between 8.5 and 62 °C: Δ 47 =0.0428±0.002∗[Formula presented]+0.0683±0.022±95%CL,TinKelvinR 2 =0.92 The slope of our calibration obtained at an acid digestion temperature of 115 °C is statistically indistinguishable from recently published calcite and dolomite clumped isotope calibrations. The intercept differs from calcite at phosphoric acid digestion temperatures of 70 and 115 °C due to a difference in phosphoric acid fractionation, highlighting the necessity of a siderite specific calibration. We performed the first survey of the clumped isotope compositions of siderites from different environmental settings at ambient temperatures including two permanently waterlogged swamp sites as modern analogues for pedogenic siderite formation in the geologic record. We conclude that pedogenic siderites form at temperatures between the Mean Annual Air Temperature (MAAT) and the summer air temperature highlighting the strong potential of siderites for paleoclimate reconstructions in continental environments. ",

keywords = "Clumped isotope thermometry, Paleosols, Siderite",

author = "{van Dijk}, Joep and Alvaro Fernandez and Storck, {Julian C.} and White, {Timothy S.} and Mark Lever and M{\"u}ller, {Inigo A.} and Stewart Bishop and Seifert, {Reto F.} and Driese, {Steven G.} and Alexey Krylov and Ludvigson, {Gregory A.} and Turchyn, {Alexandra V.} and Lin, {Chin Yik} and Chad Wittkop and Bernasconi, {Stefano M.}",

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doi = "10.1016/j.gca.2019.03.018",

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van Dijk, J, Fernandez, A, Storck, JC, White, TS, Lever, M, Müller, IA, Bishop, S, Seifert, RF, Driese, SG, Krylov, A, Ludvigson, GA, Turchyn, AV, Lin, CY, Wittkop, C & Bernasconi, SM 2019, 'Experimental calibration of clumped isotopes in siderite between 8.5 and 62 °C and its application as paleo-thermometer in paleosols', Geochimica et Cosmochimica Acta, vol. 254, pp. 1-20. https://doi.org/10.1016/j.gca.2019.03.018

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T1 - Experimental calibration of clumped isotopes in siderite between 8.5 and 62 °C and its application as paleo-thermometer in paleosols

AU - van Dijk, Joep

AU - Fernandez, Alvaro

AU - Storck, Julian C.

AU - White, Timothy S.

AU - Lever, Mark

AU - Müller, Inigo A.

AU - Bishop, Stewart

AU - Seifert, Reto F.

AU - Driese, Steven G.

AU - Krylov, Alexey

AU - Ludvigson, Gregory A.

AU - Turchyn, Alexandra V.

AU - Lin, Chin Yik

AU - Wittkop, Chad

AU - Bernasconi, Stefano M.

PY - 2019/6/1

Y1 - 2019/6/1

N2 - The clumped isotope composition of carbonates can be directly related to their formation temperature in the environment, but a robust temperature calibration for siderite is still lacking, and thus limits the applicability of this tool. Here, we present a new calibration for the clumped isotope composition of siderites precipitated with two different techniques between 8.5 and 62 °C: Δ 47 =0.0428±0.002∗[Formula presented]+0.0683±0.022±95%CL,TinKelvinR 2 =0.92 The slope of our calibration obtained at an acid digestion temperature of 115 °C is statistically indistinguishable from recently published calcite and dolomite clumped isotope calibrations. The intercept differs from calcite at phosphoric acid digestion temperatures of 70 and 115 °C due to a difference in phosphoric acid fractionation, highlighting the necessity of a siderite specific calibration. We performed the first survey of the clumped isotope compositions of siderites from different environmental settings at ambient temperatures including two permanently waterlogged swamp sites as modern analogues for pedogenic siderite formation in the geologic record. We conclude that pedogenic siderites form at temperatures between the Mean Annual Air Temperature (MAAT) and the summer air temperature highlighting the strong potential of siderites for paleoclimate reconstructions in continental environments.

AB - The clumped isotope composition of carbonates can be directly related to their formation temperature in the environment, but a robust temperature calibration for siderite is still lacking, and thus limits the applicability of this tool. Here, we present a new calibration for the clumped isotope composition of siderites precipitated with two different techniques between 8.5 and 62 °C: Δ 47 =0.0428±0.002∗[Formula presented]+0.0683±0.022±95%CL,TinKelvinR 2 =0.92 The slope of our calibration obtained at an acid digestion temperature of 115 °C is statistically indistinguishable from recently published calcite and dolomite clumped isotope calibrations. The intercept differs from calcite at phosphoric acid digestion temperatures of 70 and 115 °C due to a difference in phosphoric acid fractionation, highlighting the necessity of a siderite specific calibration. We performed the first survey of the clumped isotope compositions of siderites from different environmental settings at ambient temperatures including two permanently waterlogged swamp sites as modern analogues for pedogenic siderite formation in the geologic record. We conclude that pedogenic siderites form at temperatures between the Mean Annual Air Temperature (MAAT) and the summer air temperature highlighting the strong potential of siderites for paleoclimate reconstructions in continental environments.

KW - Clumped isotope thermometry

KW - Paleosols

KW - Siderite

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JO - Geochimica et Cosmochimica Acta

JF - Geochimica et Cosmochimica Acta

ER -

Experimental calibration of clumped isotopes in siderite between 8.5 and 62 °C and its application as paleo-thermometer in paleosols

Abstract

Funding

Keywords

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Experimental calibration of clumped isotopes in siderite between 8.5 and 62 °C and its application as paleo-thermometer in paleosols

Abstract

Funding

Keywords

Access to Document

Other files and links

Fingerprint

Cite this

Experimental calibration of clumped isotopes in siderite between 8.5 and 62 °C and its application as paleo-thermometer in paleosols