Soft X-ray spectromicroscopy study of mineral-organic matter associations in pasture soil clay fractions

Environ Sci Technol. 2014 Jun 17;48(12):6678-86. doi: 10.1021/es405485a. Epub 2014 Jun 4.

Abstract

There is a growing acceptance that associations with soil minerals may be the most important overarching stabilization mechanism for soil organic matter. However, direct investigation of organo-mineral associations has been hampered by a lack of methods that can simultaneously characterize organic matter (OM) and soil minerals. In this study, STXM-NEXAFS spectroscopy at the C 1s, Ca 2p, Fe 2p, Al 1s, and Si 1s edges was used to investigate C associations with Ca, Fe, Al, and Si species in soil clay fractions from an upland pasture hillslope. Bulk techniques including C and N NEXAFS, Fe K-edge EXAFS spectroscopy, and XRD were applied to provide additional information. Results demonstrated that C was associated with Ca, Fe, Al, and Si with no separate phase in soil clay particles. In soil clay particles, the pervasive C forms were aromatic C, carboxyl C, and polysaccharides with the relative abundance of carboxyl C and polysaccharides varying spatially at the submicrometer scale. Only limited regions in the soil clay particles had aliphatic C. Good C-Ca spatial correlations were found for soil clay particles with no CaCO3, suggesting a strong role of Ca in organo-mineral assemblage formation. Fe EXAFS showed that about 50% of the total Fe in soils was contained in Fe oxides, whereas Fe-bearing aluminosilicates (vermiculite and Illite) accounted for another 50%. Fe oxides in the soil were mainly crystalline goethite and hematite, with lesser amounts of poorly crystalline ferrihydrite. XRD revealed that soil clay aluminosilicates were hydroxy-interlayered vermiculite, Illite, and kaolinite. C showed similar correlation with Fe to Al and Si, implying a similar association of Fe oxides and aluminosilicates with organic matter in organo-mineral associations. These direct microscopic determinations can help improve understanding of organo-mineral interactions in soils.

Publication types

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

MeSH terms

  • Aluminum Silicates / chemistry*
  • Carbon / analysis
  • Cations / analysis
  • Clay
  • Elements
  • Microscopy / methods*
  • Minerals / chemistry*
  • Organic Chemicals / chemistry*
  • Particulate Matter / analysis
  • Soil / chemistry*
  • Soil Pollutants / analysis
  • Spectrum Analysis / methods*
  • X-Ray Absorption Spectroscopy
  • X-Rays

Substances

  • Aluminum Silicates
  • Cations
  • Elements
  • Minerals
  • Organic Chemicals
  • Particulate Matter
  • Soil
  • Soil Pollutants
  • Carbon
  • Clay