A New Way to Use Solid-State Carbon-13 Nuclear Magnetic Resonance Spectroscopy to Study the Sorption of Organic Compounds to Soil Organic Matter
2005
Smernik, Ronald J.
Several solid-state ¹³C nuclear magnetic resonance (NMR) techniques were used to characterize soil organic matter spiked with ¹³C-labeled organic compounds spanning a range of hydrophobicities (benzoic acid, benzophenone, naphthalene, phenanthrene, and palmitic acid). The chemical shifts of NMR resonances of the sorbed species were shifted by up to 3 ppm relative to those of the neat compounds. Sorption also resulted in increased resonance linewidth for the compounds containing a single ¹³C label, indicating the presence of a range of different chemical environments at the sites of sorption. On the other hand, sorption decreased the linewidth of the resonance of naphthalene, which was uniformly ¹³C-labeled. This was attributed to the removal of intermolecular ¹³C–¹³C dipolar coupling. Heterogeneity of the organic matter was demonstrated using the spectral editing technique proton spin relaxation editing (PSRE), which enabled the identification and quantification of charcoal-rich domains characterized by rapid rates of proton spin–lattice relaxation in the static frame (T ₁H), and humic domains characterized by slow rates of T ₁H relaxation. Furthermore it was demonstrated that the sorbed ¹³C-labeled molecules “inherit” the T ₁H “signature” of the organic matrix in their immediate vicinity. Thus PSRE on the spiked soils enabled evaluation of the relative affinity of the two domain types for the sorbate molecules. The charcoal-rich domains were shown to have a twofold to tenfold greater affinity for the organic compounds, with greater differences found for the more hydrophobic compounds.
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