Microscale characterization of sulfur speciation in lake sediments

Environ Sci Technol. 2013 Feb 5;47(3):1287-96. doi: 10.1021/es303914q. Epub 2013 Jan 16.

Abstract

Prairie pothole lakes (PPLs) are naturally sulfur-enriched wetlands in the glaciated prairie region of North America. High sulfate levels and dynamic hydrogeochemistry in combination render PPLs a unique environment to explore the speciation of sedimentary sulfur (S). The goals of this research were to define and quantify the solid-phase S pools in PPL sediments and track seasonal dynamics of S speciation. A quantitative X-ray microprobe method was developed based on S 1s X-ray absorption near-edge structure (XANES) spectroscopy and multienergy X-ray fluorescence mapping. Three S pools-pyritic S, reduced organic S (organic mono- and disulfide), and oxidized S (inorganic sulfate, ester sulfate, and sulfonate)-were identified in PPL sediments. No significant seasonal variation was evident for total S, but S speciation showed a seasonal response. During the spring-summer transition, the reduced organic S decreased from 55 to 15 mol %, with a concomitant rise in the oxidized S. During the summer-fall transition, the trend reversed and the reduced organic S grew to 75 mol % at the expense of the oxidized S. The pyritic S, on the other hand, remained relatively constant (∼22 mol %) over time. The seasonal changes in S speciation have strong potential to force the cycling of elements such as mercury in prairie wetlands.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Carbon / analysis
  • Ecosystem*
  • Geologic Sediments / chemistry*
  • Hydrogen-Ion Concentration
  • Iron / chemistry
  • Lakes / chemistry*
  • Oxidation-Reduction
  • Porosity
  • Seasons
  • Sulfates / analysis
  • Sulfides / analysis
  • Sulfides / chemistry
  • Sulfur / analysis*
  • Surface Properties
  • Thermodynamics
  • United States
  • X-Ray Absorption Spectroscopy

Substances

  • Sulfates
  • Sulfides
  • pyrite
  • Sulfur
  • Carbon
  • Iron