Quantitative solid-state 13C NMR spectroscopy of organic matter fractions in lowland rice soils

Abstract

Spin counting on solid-state 13C cross-polarization (CP) nuclear magnetic resonance (NMR) spectra of two humic fractions isolated from tropical lowland soils showed that only 32–81% of potential 13C NMR signal was detected. The observability of 13C NMR signal (Cobs) was higher in the mobile humic acid (MHA) than in the calcium humate (CaHA) fraction, and increased with increasing intensity of irrigated rice cropping. NMR observability appeared to be related to the nature of the organic carbon, with phenol- and methoxyl-rich samples having the higher values of Cobs. The Bloch decay (BD) technique provided more quantitatively reliable 13C NMR spectra, as evidenced by values of Cobs in the range 91–100% for seven of the eight humic fractions studied. The BD spectra contained considerably more aryl and carbonyl signal, and less O–alkyl and alkyl signal, with the greatest differences between CP and BD spectra observed for the samples with low Cobs(CP). The causes of low CP observability were investigated using the spectral editing technique RESTORE ( REstoration of Spectra via TCH and T One Rho (T1ρH) Editing). Rapid T1ρH relaxation was found to be primarily responsible for the under-representation of carbonyl carbon, whereas inefficient cross-polarization was primarily responsible for the under-representation of aryl carbon in CP spectra. Proton NMR relaxation rates T1H and T1ρH were found to correlate with other NMR properties and also with cropping management. Non-uniform rates of T1H relaxation in two of the CaHA fractions enabled the generation of proton spin relaxation editing subspectra.