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SOIL CHEMISTRY

Profiling Rhizosphere Chemistry: Evidence from Carbon and Nitrogen K-Edge XANES and Pyrolysis-FIMS

^a Department of Soil Science, University of Saskatchewan, 51 Campus Drive, Saskatoon, SK S7N 5A8, Canada
^b Institute for Land Use, Rostock University, Justus-von-Liebig-Weg 6, 18051 Rostock, Germany
^c Canadian Light Source Inc., 101 Perimeter Road, Saskatoon, SK S7N 0X4, Canada

^* Corresponding author (fran.walley{at}usask.ca).

The rhizosphere is a region of complex interactions among plants, soil, and microbiota and by its very nature, it presents many technical challenges to the analyst. Whereas previous studies have generally focused on root exudation in artificial systems, we compared whole-soil samples from bulk and rhizosphere soils developed under field pea (Pisum sativa L.). Synchrotron-based C and N K-edge x-ray absorption near-edge structure (XANES) spectroscopy and pyrolysis field-ionization mass-spectrometry (Py-FIMS) were used to investigate plant effects on the organic chemistry of the rhizosphere in a growth chamber experiment. Soil type appeared to play a significant role in the development of the rhizosphere. Indeed, the C and N K-edge XANES analyses revealed patterns of rhizosphere development that were strongly influenced by soil type. Relative to the bulk soil, pea rhizospheres developed on a clay soil showed increases in heterocyclic N compounds, proteins, and carboxylates. Pea rhizospheres developed on a sandy clay loam soil showed increased nitroaromatic compounds and reduced aromatics, while proteins, carbohydrates, and carboxylic compounds remained unchanged relative to the bulk soils. Pyrolysis mass spectrometry results showed that rhizosphere processes promote selective enrichment of lipid compounds (alkanes, alkenes, alkylamides, alkylaromatics, and alkyl, benzoic, and phthalic esters) with a concomitant depletion of carbohydrates, proteins, phenols, and lignins. These results suggest enhanced decomposition of labile organic matter at a molecular level in the rhizosphere, presumably as a result of enhanced microbial activity. The presence of nitroaromatic and alkylamide compounds in the rhizosphere indicates a unique cycling of N in this region. Synchrotron-based analysis of whole soils offers useful, corroborating information regarding the organic chemistry of the rhizosphere when compared with established pyrolytic techniques.

Abbreviations: FLY, fluorescence yield • PCA, principal component analysis • Py-FIMS, pyrolysis field ionization mass spectrometry • SOM, soil organic matter • TEY, total electron yield • TII, total ion intensity • XANES, x-ray absorption near-edge structure