PS 68-143 - Soil organic nitrogen speciation during 4000-year of soil and ecosystem development: Nitrogen K-edge XANES spectroscopy study

Thursday, August 11, 2011
Exhibit Hall 3, Austin Convention Center
Kang Xia, Chemistry, Mississippi State University, Mississippi State, MS and Mark A. Williams, Virginia Tech University, Blacksburg, VA
Background/Question/Methods

Organic nitrogen compounds in soils are both a source and sink for N in the terrestrial N cycle. The latest terrestrial N cycle paradigm considers soluble organic nitrogen (SON) as a rate limiting step for regulating the overall N availability in ecosystems. Despite its importance little is known about the chemical nature of organic N associated with soil minerals. Different from destructive wet chemical analysis, synchrotron-based nitrogen K-edge x-ray absorption near-edge structure (XANES) spectroscopy has been shown to be a selective, sensitive, and nondestructive method capable of providing molecular-scale information on N speciation. In this study, soils with developmental stages ranging from 0 to 4000 years were collected in a soil chronosequence.  Approximately 5000 years of deposition have formed this chronosequence of sediments originating from glacial deposits and Paleozoic bedrock underlying the lake basin. Clear patterns of vegetation succession are found where grasses tend to dominate early, while conifers and the occasional hardwood dominate at later stages of soil development. The soil samples were first rinsed with 0.01 M KCl solution to remove nitrate, ammonium, and other soluble N. The organic debris was removed by flotation and manual removal.  Nitrogen speciation in soils with and without organic debris removal were determined using N K-edge XANES. The N K-edge XANES spectra were collected at the U4B beamline of the National Synchrotron Light Source in Brookhaven National Laboratory. 

Results/Conclusions

Clear patterns of vegetation succession are found where grasses tend to dominate early, while conifers and the occasional hardwood dominate at later stages of soil development. This time series was chosen because it spans a discontinuity in vegetation that occurs at about 400 years while the change in mineralogy is linear. Mineral-associated total N increased 5 times within the initial ~400-year soil development, followed by a slow decrease within the next 3200 years. The XANES results suggested that more amide-N, indicative of proteinaceous organic N, was determined in soils with increasing soil development. Relative content of amide/peptide-N increased linearly from 30% to 65% of total N with time. This result suggests continuous mineral-sequestration of proteinous compounds during soil development. In addition to aminde-N, aromatic-N, amide-N, nitro aromatic-N, and alkyl-N were detected in the samples. Nitro-aromatic N was significantly transformed during soil development. This study indicate that application of synchrotron-based N K-edge NEXAFS is providing new and promising information about N biogeochemistry. Better understanding of amino acids-, protein-mineral interactions is needed.

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