title: The formation of sulfate and elemental sulfur aerosols under varying laboratory conditions: implications for early earth.
abstract: The presence of sulfur mass-independent fractionation (S-MIF) in sediments more than 2.45 × 10(9) years old is thought to be evidence for an early anoxic atmosphere. Photolysis of sulfur dioxide (SO(2)) by UV light with λ < 220 nm has been shown in models and some initial laboratory studies to create a S-MIF; however, sulfur must leave the atmosphere in at least two chemically different forms to preserve any S-MIF signature. Two commonly cited examples of chemically different sulfur species that could have exited the atmosphere are elemental sulfur (S(8)) and sulfuric acid (H(2)SO(4)) aerosols. Here, we use real-time aerosol mass spectrometry to directly detect the sulfur-containing aerosols formed when SO(2) either photolyzes at wavelengths from 115 to 400 nm, to simulate the UV solar spectrum, or interacts with high-energy electrons, to simulate lightning. We found that sulfur-containing aerosols form under all laboratory conditions. Further, the addition of a reducing gas, in our experiments hydrogen (H(2)) or methane (CH(4)), increased the formation of S(8). With UV photolysis, formation of S(8) aerosols is highly dependent on the initial SO(2) pressure; and S(8) is only formed at a 2% SO(2) mixing ratio and greater in the absence of a reductant, and at a 0.2% SO(2) mixing ratio and greater in the presence of 1000 ppmv CH(4). We also found that organosulfur compounds are formed from the photolysis of CH(4) and moderate amounts of SO(2). The implications for sulfur aerosols on early Earth are discussed. Key Words: S-MIF-Archean atmosphere-Early Earth-Sulfur aerosols.
authors.affiliation: Department of Chemistry and Biochemistry, University of Colorado at Boulder, Boulder, Colorado 80309, USA. dewitt@colorado.edu
authors.forename: H Langley
authors.initials: HL
authors.lastname: DeWitt
authors.forename: Christa A
authors.initials: CA
authors.lastname: Hasenkopf
authors.forename: Melissa G
authors.initials: MG
authors.lastname: Trainer
authors.forename: Delphine K
authors.initials: DK
authors.lastname: Farmer
authors.forename: Jose L
authors.initials: JL
authors.lastname: Jimenez
authors.forename: Christopher P
authors.initials: CP
authors.lastname: McKay
authors.forename: Owen B
authors.initials: OB
authors.lastname: Toon
authors.forename: Margaret A
authors.initials: MA
authors.lastname: Tolbert
mesh_terms: D000336:Aerosols; D001272:Atmosphere / Q000737:chemistry*; D018534:Earth, Planet; D005740:Gases / Q000737:chemistry; D013058:Mass Spectrometry; D010782:Photolysis; D013431:Sulfates / Q000737:chemistry; D013455:Sulfur / Q000737:chemistry*; D013458:Sulfur Dioxide / Q000737:chemistry
chemical_list: D000336:Aerosols; D005740:Gases; D013431:Sulfates; D013458:Sulfur Dioxide; D013455:Sulfur