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Sulphide oxidation and carbonate dissolution as a source of CO2 over geological timescales

Nature volume 507, pages 346–349 (2014)Cite this article

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Abstract

The observed stability of Earth’s climate over millions of years is thought to depend on the rate of carbon dioxide (CO2) release from the solid Earth being balanced by the rate of CO2 consumption by silicate weathering1. During the Cenozoic era, spanning approximately the past 66 million years, the concurrent increases in the marine isotopic ratios of strontium, osmium and lithium2,3,4 suggest that extensive uplift of mountain ranges may have stimulated CO2 consumption by silicate weathering5, but reconstructions of sea-floor spreading6 do not indicate a corresponding increase in CO2 inputs from volcanic degassing. The resulting imbalance would have depleted the atmosphere of all CO2 within a few million years7. As a result, reconciling Cenozoic isotopic records with the need for mass balance in the long-term carbon cycle has been a major and unresolved challenge in geochemistry and Earth history. Here we show that enhanced sulphide oxidation coupled to carbonate dissolution can provide a transient source of CO2 to Earth’s atmosphere that is relevant over geological timescales. Like drawdown by means of silicate weathering, this source is probably enhanced by tectonic uplift, and so may have contributed to the relative stability of the partial pressure of atmospheric CO2 during the Cenozoic. A variety of other hypotheses8,9,10 have been put forward to explain the ‘Cenozoic isotope-weathering paradox’, and the evolution of the carbon cycle probably depended on multiple processes. However, an important role for sulphide oxidation coupled to carbonate dissolution is consistent with records of radiogenic isotopes2,3, atmospheric CO2 partial pressure11,12 and the evolution of the Cenozoic sulphur cycle, and could be accounted for by geologically reasonable changes in the global dioxygen cycle, suggesting that this CO2 source should be considered a potentially important but as yet generally unrecognized component of the long-term carbon cycle.

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Figure 1: CO2 uptake (green bars) and release (red bars) rates calculated for the Mackenzie River17,22, the Liwu River20,21 and the Ganges–Brahmaputra (G–B)19.
Figure 2: Conceptual model of the timescale of CO2 release associated with the contrasting timescales of sulphide and carbonate burial.
Figure 3: Comparison of the isotope mass balance model calculations with proxy records for changes in the Cenozoic C cycle.
Figure 4: Trade-off between CO2 release and O2 consumption as a result of sulphide oxidation.

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Acknowledgements

Support for this work comes from a USC College Fellowship and a C-DEBI Graduate Fellowship to M.A.T., NSF funding (NSF-EAR/GLD-1053504 and EAR/GLTG-1227192) to A.J.W., and National Natural Science Foundation of China funding (grant nos 41173105, 41102103 and 41321062) to G.L. This is C-DEBI contribution #197.

Author information

Authors and Affiliations

  1. Department of Earth Sciences, University of Southern California, Los Angeles, 90089, California, USA

    Mark A. Torres & A. Joshua West

  2. Department of Earth Sciences, MOE Key Laboratory of Surficial Geochemistry, Nanjing University, 163 Xianlindadao, Nanjing 210046, China,

    Gaojun Li

Authors
  1. Mark A. Torres
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Contributions

M.A.T. and A.J.W. designed the study, the conceptual model experiments and the sulphur isotope modelling. G.L. contributed the isotope mass balance model. M.A.T. and A.J.W. wrote the manuscript.

Corresponding authors

Correspondence to Mark A. Torres, A. Joshua West or Gaojun Li.

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The authors declare no competing financial interests.

Extended data figures and tables

Extended Data Figure 1 Riverine input fluxes and calculated pyrite burial fluxes from 0 to 50 Myr ago for constant δ34S values of riverine input and Δpyrite-seawater.

Solid and dashed black lines indicate the total and pyrite-derived input fluxes of sulphate from the Li and Elderfield10 model, respectively. The green band indicates the range of calculated pyrite burial fluxes for experiments where the δ34S value of riverine S flux was equal to 10‰ and Δpyrite-seawater was varied between −30 and −50‰. The pink band indicates the range of calculated pyrite burial fluxes for experiments where the δ34S value of riverine S flux was equal to 5‰ and Δpyrite-seawater was varied between −30 and −50‰. The blue band indicates the range of calculated pyrite burial fluxes for experiments where the δ34S value of riverine was equal to 0‰ and Δpyrite-seawater was varied between −30 and −50‰. The khaki bar indicates the range of pyrite burial fluxes estimated from the pyrite content of marine sediments by ref. 40.

Extended Data Figure 2 Calculated Δpyrite-seawater values from 0 to 30 Myr ago for constant δ34S values of riverine input and pyrite burial fluxes.

The solid and dashed black lines indicate the average and minimum Δpyrite-seawater values for the Phanerozoic based on the isotopic offset between coeval marine sulphate and sulphide minerals38,45. The thickness of the solid line reflects 1 s.d. of the average Δpyrite-seawater from ref. 38. The green band indicates the range of calculated Δpyrite-seawater values for experiments where the pyrite burial flux was 1 × 1018 mol S Myr−1 and the δ34S value of riverine was varied between 0 and 10‰. The blue band indicates the range of calculated Δpyrite-seawater values for experiments where the pyrite burial flux was 0.67 × 1018 mol S Myr−1 and the δ34S value of riverine was varied between 0 and 10‰. The brown band indicates the range of calculated Δpyrite-seawater values for experiments where the pyrite burial flux was 0.22 × 1018 mol S Myr−1 and the δ34S value of riverine was varied between 0 and 10‰.

Extended Data Figure 3 Calculated δ34S values of riverine input from 0 to 30 Myr ago for constant Δpyrite-seawater values and pyrite burial fluxes.

The solid black line on the vertical axis indicates the range of estimates for the modern δ34S value of riverine input27,40. The green band indicates the range of calculated δ34S values of riverine input for experiments where the pyrite burial flux was 1 × 1018 mol S Myr−1 and Δpyrite-seawater was varied between −30 and −50‰. The blue band indicates the range of calculated δ34S values of riverine input for experiments where the pyrite burial flux was 0.67 × 1018 mol S Myr−1 and Δpyrite-seawater was varied between −30 and −50‰. The brown band indicates the range of calculated δ34S values of riverine input for experiments where the pyrite burial flux was 0.22 × 1018 mol S Myr−1 and Δpyrite-seawater was varied between −30 and −50‰.

Extended Data Figure 4 Integrated O2 consumption and CO2 production implied by the S cycle inverse model for different input parameters.

The O2 consumption values are presented in molar units. Importantly, the implied values ignore other processes affecting the O2 budget (for example changes in the organic C cycle). Negative values of both CO2 and O2 consumption reflect net sulphide burial. Independent estimates of the δ34S of riverine input40,46 and the average Δpyrite-seawater (ref. 38) correspond to the parameter combinations that produce net sulphide oxidation (that is, positive values) and are marked with stars. a, The model results integrated from 0 to 50 Myr ago. b, The model results integrated from 0 to 15 Myr ago following the results of the Li and Elderfield10 model, which suggests that sulphide oxidation acted at least in part to balance enhanced CO2 consumption over this time period. The dashed horizontal lines represent the CO2 release required to compensate fully for a 10% (blue), 25% (purple) or 50% (orange) increase in continental silicate weathering that occurred linearly over the past 15 Myr assuming a modern flux of 3.5 × 1018 mol Myr−1 (Methods). The 25% increase corresponds to the increase predicted by the Li and Elderfield10 mass balance model.

Extended Data Table 1 CO2 consumption and release rates in modern river systems17,19,20,21,22
Full size table

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Torres, M., West, A. & Li, G. Sulphide oxidation and carbonate dissolution as a source of CO2 over geological timescales. Nature 507, 346–349 (2014). https://doi.org/10.1038/nature13030

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