Bulk and grain-scale minor sulfur isotope data reveal complexities in the dynamics of Earth's oxygenation

Proc Natl Acad Sci U S A. 2022 Mar 29;119(13):e2025606119. doi: 10.1073/pnas.2025606119. Epub 2022 Mar 21.

Abstract

SignificanceThe permanent disappearance of mass-independent sulfur isotope fractionation (S-MIF) from the sedimentary record has become a widely accepted proxy for atmospheric oxygenation. This framework, however, neglects inheritance from oxidative weathering of pre-existing S-MIF-bearing sedimentary sulfide minerals (i.e., crustal memory), which has recently been invoked to explain apparent discrepancies within the sulfur isotope record. Herein, we demonstrate that such a crustal memory effect does not confound the Carletonville S-isotope record; rather, the pronounced Δ33S values identified within the Rooihoogte Formation represent the youngest known unequivocal oxygen-free photochemical products. Previously observed 33S-enrichments within the succeeding Timeball Hill Formation, however, contrasts with our record, revealing kilometer-scale heterogeneities that highlight significant uncertainties in our understanding of the dynamics of Earth's oxygenation.

Keywords: Transvaal Basin; atmospheric oxygenation; mass-independent S-isotope fractionation; quadruple sulfur isotope.