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Variations in atmospheric sulphur chemistry on early Earth linked to volcanic activity

Nature Geoscience volume 5, pages 668–674 (2012)Cite this article

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Abstract

Volcanism on early Earth should have had an impact on atmospheric chemistry, but that impact can be challenging to reconstruct. The isotopic composition of sulphur contained in rocks deposited more than 2.45 billion years (Gyr) ago shows both mass-dependent (as denoted by δ34S) and mass-independent (Δ33S) isotopic fractionation. This sulphur is predominantly in the form of suphides. These sulphides show a positive correlation between δ34S and Δ33S between 4.0 and 2.45 Gyr ago. Sulphates deposited episodically between about 3.5 and 3.2 Gyr ago indicate a more homogeneous sulphur reservoir and show no correlation to the sulphide trend. Here we report sulphur isotope values of sulphide from volcanic ash layers in the 3.2-Gyr-old Mapepe Formation of South Africa. We find a δ34S–Δ33S relationship that deviates from previous sulphide isotope records and instead overlaps with the range of values reported for sulphates. Coexisting sulphates and sulphides of a similar age found in Australia and India show a similar array of δ34S–Δ33S values. We suggest that the occurrence of this δ34S–Δ33S array reflects widespread, ultraviolet-light-triggered photodissociation of sulphur dioxide that was released into the atmosphere by short-lived but intense bursts of subaerial volcanic activity.

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Figure 1: Barberton Barite Drilling Project (BBDP).
Figure 2: Δ33S–δ34S distribution of Archaean sulphides and sulphates.
Figure 3: Formation of sulphate–sulphide deposits in the early Archaean.
Figure 4: The Archaean sulphur cycle.

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Acknowledgements

P.P. acknowledges support from the Centre National de la Recherche Scientifique, the Institut de Physique du Globe de Paris and the African Earth Network Observatory for carrying out the BBDP and from grants from the ANR (eLIFE and eLIFE2) and Labex UnivEarths. We thank D. Mangin and O. Boudouma for assistance with IMS and scanning electron microscopy, D. Rumble for corrections on an early version of the manuscript and E. Muller for providing Supplementary Fig. S6. This is Institut de Physique du Globe de Paris contribution number 3302.

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Authors and Affiliations

  1. Equipe Géobiosphère, Institut de Physique du Globe—Sorbonne Paris Cité, Université Paris Diderot, CNRS, 1 place Jussieu, 75238 Paris, France

    Pascal Philippot & Mark van Zuilen

  2. Centre de Recherches Pétrographiques et Géochimiques, 15 rue Notre Dame des Pauvres, 54500 Vandœuvre-les-Nancy, France

    Claire Rollion-Bard

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  1. Pascal Philippot
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Contributions

P.P. and M.v.Z. carried out the BBDP. P.P. carried out the logging of the BBDP core and selected the samples for SIMS and SEM analyses. P.P. and M.v.Z. collected SIMS data. P.P. collected SEM data. P.P., M.v.Z. and C.R-B. analysed the results and wrote the paper.

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Correspondence to Pascal Philippot.

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Philippot, P., van Zuilen, M. & Rollion-Bard, C. Variations in atmospheric sulphur chemistry on early Earth linked to volcanic activity. Nature Geosci 5, 668–674 (2012). https://doi.org/10.1038/ngeo1534

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