title: Multiple sulfur-isotope signatures in Archean sulfates and their implications for the chemistry and dynamics of the early atmosphere.
abstract: Sulfur isotopic anomalies (∆(33)S and ∆(36)S) have been used to trace the redox evolution of the Precambrian atmosphere and to document the photochemistry and transport properties of the modern atmosphere. Recently, it was shown that modern sulfate aerosols formed in an oxidizing atmosphere can display important isotopic anomalies, thus questioning the significance of Archean sulfate deposits. Here, we performed in situ 4S-isotope measurements of 3.2- and 3.5-billion-year (Ga)-old sulfates. This in situ approach allows us to investigate the diversity of Archean sulfate texture and mineralogy with unprecedented resolution and from then on to deconvolute the ocean and atmosphere Archean sulfur cycle. A striking feature of our data is a bimodal distribution of δ(34)S values at ∼+5‰ and +9‰, which is matched by modern sulfate aerosols. The peak at +5‰ represents barite of different ages and host-rock lithology showing a wide range of ∆(33)S between -1.77‰ and +0.24‰. These barites are interpreted as primary volcanic emissions formed by SO2 photochemical processes with variable contribution of carbonyl sulfide (OCS) shielding in an evolving volcanic plume. The δ(34)S peak at +9‰ is associated with non-(33)S-anomalous barites displaying negative ∆(36)S values, which are best interpreted as volcanic sulfate aerosols formed from OCS photolysis. Our findings confirm the occurrence of a volcanic photochemical pathway specific to the early reduced atmosphere but identify variability within the Archean sulfate isotope record that suggests persistence throughout Earth history of photochemical reactions characteristic of the present-day stratosphere.
authors.affiliation: Institut de Physique du Globe de Paris, Université Paris Diderot, Sorbonne Paris Cité, UMR 7154 CNRS, F-75238 Paris Cédex 05, France emuller@ipgp.fr philippot@ipgp.fr.
authors.forename: Élodie
authors.initials: É
authors.lastname: Muller
authors.affiliation: Institut de Physique du Globe de Paris, Université Paris Diderot, Sorbonne Paris Cité, UMR 7154 CNRS, F-75238 Paris Cédex 05, France emuller@ipgp.fr philippot@ipgp.fr.
authors.forename: Pascal
authors.initials: P
authors.lastname: Philippot
authors.affiliation: Institut de Physique du Globe de Paris, Université Paris Diderot, Sorbonne Paris Cité, UMR 7154 CNRS, F-75238 Paris Cédex 05, France.
authors.forename: Claire
authors.initials: C
authors.lastname: Rollion-Bard
authors.affiliation: Institut de Physique du Globe de Paris, Université Paris Diderot, Sorbonne Paris Cité, UMR 7154 CNRS, F-75238 Paris Cédex 05, France.
authors.forename: Pierre
authors.initials: P
authors.lastname: Cartigny
keywords: Archean; atmosphere photochemistry; sulfate; sulfur isotopes