The evolution of the global carbon and silicon cycles is thought to have contributed to the long-term stability of Earth’s climate1,2,3. Many questions remain, however, regarding the feedback mechanisms at play, and there are limited quantitative constraints on the sources and sinks of these elements in Earth’s surface environments4,5,6,7,8,9,10,11,12. Here we argue that the lithium-isotope record can be used to track the processes controlling the long-term carbon and silicon cycles. By analysing more than 600 shallow-water marine carbonate samples from more than 100 stratigraphic units, we construct a new carbonate-based lithium-isotope record spanning the past 3 billion years. The data suggest an increase in the carbonate lithium-isotope values over time, which we propose was driven by long-term changes in the lithium-isotopic conditions of sea water, rather than by changes in the sedimentary alterations of older samples. Using a mass-balance modelling approach, we propose that the observed trend in lithium-isotope values reflects a transition from Precambrian carbon and silicon cycles to those characteristic of the modern. We speculate that this transition was linked to a gradual shift to a biologically controlled marine silicon cycle and the evolutionary radiation of land plants13,14.
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Jaffrés, J. B. D., Shields, G. A. & Wallmann, K. The oxygen isotope evolution of seawater: a critical review of a long-standing controversy and an improved geological water cycle model for the past 3.4 billion years. Earth Sci. Rev. 83, 83–122 (2007).
Berner, R. A., Lasaga, A. C. & Garrels, R. M. Carbonate-silicate geochemical cycle and its effect on atmospheric carbon dioxide over the past 100 million years. Am. J. Sci. 283, 641–683 (1983).
West, A. J., Galy, A. & Bickle, M. Tectonic and climatic controls on silicate weathering. Earth Planet. Sci. Lett. 235, 211–228 (2005).
Isson, T. T. et al. Evolution of the global carbon cycle and climate regulation on Earth. Glob. Biogeochem. Cycles 34, 1–28 (2020).
Hilton, R. G. & West, A. J. Mountains, erosion and the carbon cycle. Nat. Rev. Earth Environ. 1, 284–299 (2020).
Mills, B., Lenton, T. M. & Watson, A. J. Proterozoic oxygen rise linked to shifting balance between seafloor and terrestrial weathering. Proc. Natl Acad. Sci. USA 111, 9073–9078 (2014).
Coogan, L. A., Gillis, K. M., Pope, M. & Spence, J. The role of low-temperature (off-axis) alteration of the oceanic crust in the global Li-cycle: insights from the Troodos ophiolite. Geochim. Cosmochim. Acta 203, 201–215 (2017).
Isson, T. T. & Planavsky, N. J. Reverse weathering as a long-term stabilizer of marine pH and planetary climate. Nature 560, 471–475 (2018).
Krissansen-Totton, J. & Catling, D. C. Constraining climate sensitivity and continental versus seafloor weathering using an inverse geological carbon cycle model. Nat. Commun. 8, 15423 (2017).
Krissansen-Totton, J. & Catling, D. C. A coupled carbon-silicon cycle model over Earth history: reverse weathering as a possible explanation of a warm mid-Proterozoic climate. Earth Planet. Sci. Lett. 537, 116181 (2020).
Keller, C. K. & Wood, B. D. Possibility of chemical weathering before the advent of vascular land plants. Nature 364, 223–225 (1993).
Ibarra, D. E. et al. Modeling the consequences of land plant evolution on silicate weathering. Am. J. Sci. 319, 1–43 (2019).
McMahon, W. J. & Davies, N. S. Evolution of alluvial mudrock forced by early land plants. Science 359, 1022–1024 (2018).
Berner, R. A. & Kothavala, Z. GEOCARB III: a revised model of atmospheric CO2 over Phanerozoic time. Am. J. Sci. 301, 182–204 (2001).
Dellinger, M. et al. Riverine Li isotope fractionation in the Amazon River basin controlled by the weathering regimes. Geochim. Cosmochim. Acta 164, 71–93 (2015).
Vigier, N. et al. Quantifying Li isotope fractionation during smectite formation and implications for the Li cycle. Geochim. Cosmochim. Acta 72, 780–792 (2008).
Sauzéat, L., Rudnick, R. L., Chauvel, C., Garçon, M. & Tang, M. New perspectives on the Li isotopic composition of the upper continental crust and its weathering signature. Earth Planet. Sci. Lett. 428, 181–192 (2015).
Misra, S. & Froelich, P. N. Lithium isotope history of Cenozoic seawater: changes in silicate weathering and reverse weathering. Science 335, 818–823 (2012).
Pogge von Strandmann, P. A. E. & Henderson, G. M. The Li isotope response to mountain uplift. Geology 43, 67–70 (2015).
Pogge von Strandmann, P. A. E. et al. Assessing bulk carbonates as archives for seawater Li isotope ratios. Chem. Geol. 530, 119338 (2019).
Washington, K. E. et al. Lithium isotope composition of modern and fossilized Cenozoic brachiopods. Geology 48, 1058–1061 (2020).
Fantle, M. S., Barnes, B. D. & Lau, K. V. The role of diagenesis in shaping the geochemistry of the marine carbonate record. Annu. Rev. Earth Planet. Sci. 48, 549–583 (2020).
Dellinger, M. et al. The effects of diagenesis on lithium isotope ratios of shallow marine carbonates. Am. J. Sci. 320, 150–184 (2020).
Hood, A. van S. & Wallace, M. W. Synsedimentary diagenesis in a Cryogenian reef complex: ubiquitous marine dolomite precipitation. Sedim. Geol. 255–256, 56–71 (2012).
Blättler, C. L. & Higgins, J. A. Testing Urey’s carbonate–silicate cycle using the calcium isotopic composition of sedimentary carbonates. Earth Planet. Sci. Lett. 479, 241–251 (2017).
Ahm, A. C. et al. An early diagenetic deglacial origin for basal Ediacaran “cap dolostones”. Earth Planet. Sci. Lett. 506, 292–307 (2019).
Hoffman, P. F. & Lamothe, K. G. Seawater-buffered diagenesis, destruction of carbon isotope excursions, and the composition of DIC in Neoproterozoic oceans. Proc. Natl Acad. Sci. USA 116, 18874–18879 (2019).
Ahm, A. S. C., Bjerrum, C. J., Blättler, C. L., Swart, P. K. & Higgins, J. A. Quantifying early marine diagenesis in shallow-water carbonate sediments. Geochim. Cosmochim. Acta 236, 140–159 (2018).
Higgins, J. A. et al. Mineralogy, early marine diagenesis, and the chemistry of shallow-water carbonate sediments. Geochim. Cosmochim. Acta 220, 512–534 (2018).
Hathorne, E. C. & James, R. H. Temporal record of lithium in seawater: a tracer for silicate weathering? Earth Planet. Sci. Lett. 246, 393–406 (2006).
Hall, J. M., Chan, L. H., McDonough, W. F. & Turekian, K. K. Determination of the lithium isotopic composition of planktic foraminifera and its application as a paleo-seawater proxy. Mar. Geol. 217, 255–265 (2005).
Crockford, P. W. et al. Reconstructing Neoproterozoic seawater chemistry from early diagenetic dolomite. Geology 49, 442–446 (2021).
Ullmann, C. V. et al. Partial diagenetic overprint of Late Jurassic belemnites from New Zealand: implications for the preservation potential of δ7Li values in calcite fossils. Geochim. Cosmochim. Acta 120, 80–96 (2013).
Veizer, J. in Encyclopedia of Paleoclimatology and Ancient Environments (ed. Gornitz, V.) 923–926 (Springler, 2009).
Hood, A. van S. & Wallace, M. W. Neoproterozoic marine carbonates and their paleoceanographic significance. Global Planet. Change 160, 28–45 (2018).
Jeffcoate, A. B., Elliott, T., Thomas, A. & Bouman, C. Precise, small sample size determinations of lithium isotopic compositions of geological reference materials and modern seawater by MC-ICP-MS. Geostand. Geoanal. Res. 28, 161–172 (2004).
Galili, N. et al. The geologic history of seawater oxygen isotopes from marine iron oxides. Science 365, 469–473 (2019).
Coogan, L. A. & Dosso, S. An internally consistent, probabilistic, determination of ridge-axis hydrothermal fluxes from basalt-hosted systems. Earth Planet. Sci. Lett. 323–324, 92–101 (2012).
O’Neill, C., Lenardic, A., Höink, T. & Coltice, N. in Comparative Climatology of Terrestrial Planets (eds Mackwell, S. J., Simon-Miller, A. A., Harder, J. W. & Bullock, M. A.) 473–486 (Univ. Arizona Press, 2013).
Korenaga, J. Initiation and evolution of plate tectonics on Earth: theories and observations. Annu. Rev. Earth Planet. Sci. 41, 117–151 (2013).
Rafiei, M. & Kennedy, M. Weathering in a world without terrestrial life recorded in the Mesoproterozoic Velkerri Formation. Nat. Commun. 10, 3448 (2019).
Clark, S. K. & Johnson, T. M. Effective isotopic fractionation factors for solute removal by reactive sediments: a laboratory microcosm and slurry study. Environ. Sci. Technol. 42, 7850–7855 (2008).
Conley, D. J. et al. Biosilicification drives a decline of dissolved Si in the oceans through geologic time. Front. Mar. Sci. 4, 397 (2017).
Pogge von Strandmann, P. A. E. et al. Global climate stabilisation by chemical weathering during the Hirnantian glaciation. Geochem. Perspect. Lett. 3, 230–237 (2017).
Lechler, M., Pogge von Strandmann, P. A. E., Jenkyns, H. C., Prosser, G. & Parente, M. Lithium-isotope evidence for enhanced silicate weathering during OAE 1a (Early Aptian Selli event). Earth Planet. Sci. Lett. 432, 210–222 (2015).
Pogge von Strandmann, P. A. E., Jenkyns, H. C. & Woodfine, R. G. Lithium isotope evidence for enhanced weathering during Oceanic Anoxic Event 2. Nat. Geosci. 6, 668–672 (2013).
Shields, G. & Veizer, J. Precambrian marine carbonate isotope database: version 1.1. Geochem. Geophys. Geosyst. 3, https://doi.org/10.1029/2001GC000266 (2002).
McArthur, J. M., Howarth, R. J. & Shields-Zhou, G. A. in A Geologic Time Scale 2012 (eds Gradstein, F., Ogg, J., Schmitz, M. & Ogg, G.) 127–144 (Cambridge Univ. Press, 2012).
Holland, H. D. Why the atmosphere became oxygenated: a proposal. Geochim. Cosmochim. Acta 73, 5241–5255 (2009).
Tajika, E. & Matsui, T. Evolution of terrestrial proto-CO2 atmosphere coupled with thermal history of the earth. Earth Planet. Sci. Lett. 113, 251–266 (1992).
N.J.P. acknowledges funding from the Alternative Earths NASA Astrobiology Institute and the Packard Foundation. P.A.E.P.v.S. was funded by a European Research Council (ERC) consolidator grant (682760 CONTROLPASTCO2). A.v.S.H. acknowledges funding from an Australian Research Council (ARC) Discovery Early Career Researcher Award (DECRA; DE190100988). B.K.-A. acknowledges financial support from the Yale Institute for Biospheric Studies. We thank J. Utrup, S. H. Butts and the Yale Peabody Museum of Natural History for providing brachiopods and carbonate samples.
The authors declare no competing interests.
Peer review information Nature thanks Jeremy Caves Rugenstein and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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The file contains Supplementary Figures 1 – 29; Supplementary Tables 1 – 3; Supplementary Methods; Supplementary Discussion; Global lithium isotope mass balance; Diagenetic modelling and Supplementary References.
Description of the samples analysed in this study at a) Yale University; b) Oxford and University College London.
Geochemical data generated in this study: a) δ7Li (in ‰), Li, Mg, Al, Ca, Ti, Mn, Rb, Sr, Pb concentrations (in ppm) and δ44/40Ca (in ‰) of the samples analysed at Yale University; b) δ7Li (in ‰), Li/Ca, Al/Ca, Mn/Ca, Sr/Ca and Mg/Ca elemental ratios of the samples analysed at Oxford and University College London.
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Kalderon-Asael, B., Katchinoff, J.A.R., Planavsky, N.J. et al. A lithium-isotope perspective on the evolution of carbon and silicon cycles. Nature 595, 394–398 (2021). https://doi.org/10.1038/s41586-021-03612-1