Articles | Volume 16, issue 21
Atmos. Chem. Phys., 16, 13389–13398, 2016
Atmos. Chem. Phys., 16, 13389–13398, 2016

Research article 31 Oct 2016

Research article | 31 Oct 2016

Composition and oxidation state of sulfur in atmospheric particulate matter

Amelia F. Longo1, David J. Vine2, Laura E. King1, Michelle Oakes3, Rodney J. Weber1, Lewis Gregory Huey1, Armistead G. Russell1, and Ellery D. Ingall1 Amelia F. Longo et al.
  • 1School of Earth and Atmospheric Sciences, Georgia Institute of Technology, 311 Ferst Drive, Atlanta, GA 30332, USA
  • 2Advanced Photon Source, Argonne National Laboratory, 9700 S. Cass Avenue, Argonne, IL 60439, USA
  • 3Tennessee Department of Environment and Conservation, Division of Air Pollution Control, Nashville, TN 37206, USA

Abstract. The chemical and physical speciation of atmospheric sulfur was investigated in ambient aerosol samples using a combination of sulfur near-edge x-ray fluorescence spectroscopy (S-NEXFS) and X-ray fluorescence (XRF) microscopy. These techniques were used to determine the composition and oxidation state of sulfur in common primary emission sources and ambient particulate matter collected from the greater Atlanta area. Ambient particulate matter samples contained two oxidation states: S0 and S+VI. Ninety-five percent of the individual aerosol particles (> 1 µm) analyzed contain S0. Linear combination fitting revealed that S+VI in ambient aerosol was dominated by ammonium sulfate as well as metal sulfates. The finding of metal sulfates provides further evidence for acidic reactions that solubilize metals, such as iron, during atmospheric transport. Emission sources, including biomass burning, coal fly ash, gasoline, diesel, volcanic ash, and aerosolized Atlanta soil, and the commercially available bacterium Bacillus subtilis, contained only S+VI. A commercially available Azotobacter vinelandii sample contained approximately equal proportions of S0 and S+VI. S0 in individual aerosol particles most likely originates from primary emission sources, such as aerosolized bacteria or incomplete combustion.

Short summary
New synchrotron-based techniques were applied to characterize the oxidation state and composition of sulfur in ambient aerosol and emission sources. Individual particles were found to contain surprisingly high levels of elemental sulfur, a form of sulfur found in only one of the emission sources analyzed. We also show metal sulfates as a key component of urban aerosols. These metal sulfate phases are highly soluble and are indicative of acidic processes transforming metals in the environment.
Final-revised paper