title: Large sulfur-isotope anomaly in nonvolcanic sulfate aerosol and its implications for the Archean atmosphere.
abstract: Sulfur-isotopic anomalies have been used to trace the evolution of oxygen in the Precambrian atmosphere and to document past volcanic eruptions. High-precision sulfur quadruple isotope measurements of sulfate aerosols extracted from a snow pit at the South Pole (1984-2001) showed the highest S-isotopic anomalies (Δ(33)S = +1.66‰ and Δ(36)S = +2‰) in a nonvolcanic (1998-1999) period, similar in magnitude to Pinatubo and Agung, the largest volcanic eruptions of the 20th century. The highest isotopic anomaly may be produced from a combination of different stratospheric sources (sulfur dioxide and carbonyl sulfide) via SOx photochemistry, including photoexcitation and photodissociation. The source of anomaly is linked to super El Niño Southern Oscillation (ENSO) (1997-1998)-induced changes in troposphere-stratosphere chemistry and dynamics. The data possess recurring negative S-isotope anomalies (Δ(36)S = -0.6 ± 0.2‰) in nonvolcanic and non-ENSO years, thus requiring a second source that may be tropospheric. The generation of nonvolcanic S-isotopic anomalies in an oxidizing atmosphere has implications for interpreting Archean sulfur deposits used to determine the redox state of the paleoatmosphere.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, CA 92093;
authors.forename: Robina
authors.initials: R
authors.lastname: Shaheen
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, CA 92093;
authors.forename: Mariana M
authors.initials: MM
authors.lastname: Abaunza
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, CA 92093;
authors.forename: Teresa L
authors.initials: TL
authors.lastname: Jackson
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, CA 92093;Pacific Ridge School, Carlsbad, CA 92009;
authors.forename: Justin
authors.initials: J
authors.lastname: McCabe
authors.affiliation: Laboratoire de Glaciologie et de Géophysique de l'Environnement, Centre National de la Recherche Scientifique, Unité Mixte de Recherche 5183, F-38041 Grenoble, France; andLaboratoire de Glaciologie et de Géophysique de l'Environnement, Université Grenoble Alpes, Unité Mixte de Recherche 5183, F-38041 Grenoble, France.
authors.forename: Joël
authors.initials: J
authors.lastname: Savarino
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, CA 92093; mthiemens@ucsd.edu.
authors.forename: Mark H
authors.initials: MH
authors.lastname: Thiemens
keywords: UV photolysis; sulfur isotopes
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