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- Publisher
- Wiley
- Copyright
- Copyright © 2022 John Wiley & Sons Ltd
- ISSN
- 1472-4677
- eISSN
- 1472-4669
- DOI
- 10.1111/gbi.12486
- Publisher site
- See Article on Publisher Site
Abstract
Sedimentary records of superheavy pyrites in Phanerozoic and Proterozoic successions (i.e., extremely positive δ34Spyrite values together with higher δ34Spyrite than coeval δ34SCAS) are mostly interpreted as resulting either from secondary postdepositional processes or from multiple redox reactions between sulfate and sulfide in stratified sulfate‐poor environments. We report here the first observation of strongly positive δ34S values for both dissolved sulfate and sulfide (average δ34Sdiss.sulfate value of 34.6‰ and δ34Sdiss.sulfide values of 36.7‰) compared to the present‐day seawater δ34Sdiss.sulfate (~21‰), with a negative apparent fractionation between sulfate and sulfide (∆34Sdiss.sulfate‐diss.sulfide ~ −2.1 ± 1.4‰), in the sulfate‐poor (<3 mm) modern thalassohaline lacustrine system Dziani Dzaha (Mayotte, Indian Ocean). Overall, surface sediments faithfully record the water column isotopic signatures including a mainly negative ∆34Ssed.sulfate‐sed.sulfide (−4.98 ± 4.5‰), corresponding to the definition of superheavy pyrite documented in the rock record. We propose that in the Dziani Dzaha this superheavy pyrite signature results from a two‐stage evolution of the sulfur biogeochemical cycle. In a first stage, the sulfur cycle would have been dominated by sulfate from initially sulfate‐rich marine waters. Overtime, Raleigh distillation by microbial sulfate reduction coupled with sulfide burial in the sediment would have progressively enriched in 34S the water column residual sulfate. In a second still active stage, quantitative sulfate reduction not only occurs below the halocline during stratified periods but also in the whole water column during fully anoxic episodes. Sulfates are then regenerated by partial oxidation of sulfides as the oxic–anoxic interface moves downward. These results demonstrate that the atypical superheavy pyrite isotope signature does not necessarily require postdepositional or secondary oxidative processes and can result from primary processes in restricted sulfate‐poor and highly productive environments analogous to the Dziani Dzaha.
Journal
Geobiology – Wiley
Published: May 1, 2022
Keywords: microbial sulfate reduction; modern analogue; multiple sulfur isotopes; sulfide oxidation; superheavy pyrites