Analytical and Bioanalytical Chemistry

, Volume 408, Issue 2, pp 651–655 | Cite as

Application of 13C ramp CPMAS NMR with phase-adjusted spinning sidebands (PASS) for the quantitative estimation of carbon functional groups in natural organic matter

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Abstract

The composition of carbon (C) functional groups in natural organic matter (NOM), such as dissolved organic matter, soil organic matter, and humic substances, is frequently estimated using solid-state 13C NMR techniques. A problem associated with quantitative analysis using general cross polarization/magic angle spinning (CPMAS) spectra is the appearance of spinning side bands (SSBs) split from the original center peaks of sp 2 hybridized C species (i.e., aromatic and carbonyl C). Ramp CP/phase-adjusted side band suppressing (PASS) is a pulse sequence that integrates SSBs separately and quantitatively recovers them into their inherent center peaks. In the present study, the applicability of ramp CP/PASS to NOM analysis was compared with direct polarization (DPMAS), another quantitative method but one that requires a long operation time, and/or a ramp CP/total suppression side band (ramp CP/TOSS) technique, a popular but non-quantitative method for deleting SSBs. The test materials were six soil humic acid samples with various known degrees of aromaticity and two fulvic acids. There were no significant differences in the relative abundance of alkyl C, O-alkyl C, and aromatic C between the ramp CP/PASS and DPMAS methods, while the signal intensities corresponding to aromatic C in the ramp CP/TOSS spectra were consistently less than the values obtained in the ramp CP/PASS spectra. These results indicate that ramp CP/PASS can be used to accurately estimate the C composition of NOM samples.

Keywords

Solid-state 13C NMR Phase-adjusted side band suppressing (PASS) Cross polarization/magic angle spinning (CPMAS) Direct polarization (DPMAS) Carbon functional groups Humic substances 
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Notes

Acknowledgments

This research was supported by a Grant-in-Aid for Scientific Research (No. 20380043) from the Japan Society for the Promotion of Science. The authors thank Dr. T. Nakai, JEOL RESONANCE, for his great support in acquiring PASS sequence and technical official, Y. Maeda, Nagoya University, for his kind support in using an NMR spectrometer ECA 700. The authors thank Dr. Z. Zhong and Dr. P. G. Hatcher, Old Dominion University, for their great support in the measurement of 13C DPMAS NMR spectra. The authors also thank two anonymous reviewers for providing critical comments and valuable suggestions.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no competing interests.

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Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  1. 1.Graduate School of Bioagricultural SciencesNagoya UniversityNagoyaJapan
  2. 2.Graduate School of Environmental StudiesNagoya UniversityNagoyaJapan

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