Relative proportions of organic carbon functional groups in biochars as influenced by spectral data collection and processing

Solid-state C-13 Nuclear Magnetic Resonance (NMR) and synchrotron-based X-ray Absorption Near-Edge Structure (XANES) have applications for determining the relative proportions of organic C functional groups in materials. Spectral data obtained by NMR is typically processed using integration (INTEG) whereas XANES spectral data is typically processed using deconvolution (DECONV). The objective of this study was to examine the impact of spectral data collection and processing on the estimated relative proportions of organic C functional groups in biochars. Biochars showed large variations in aromatic C (45-97%), alkyl C (0-23%), O-alkyl C (1-41%), phenolic C (0-20%) and carboxylic C (0-20%). NMR had a better ability than XANES to differentiate % aromatic C across biochars, and the mean % aromatic C was always greater for NMR-INTEG and NMR-DECONV than for XANES-INTEG or XANES-DECONV. NMR-INTEG showed significant associations with NMR-DECONV and XANES-INTEG for % aromatic C and alkyl C, but there were no significant associations between NMR and XANES for % O-alkyl C, phenolic C and carboxylic C. As well, there was no association between NMR-INTEG and XANES-DECONV for any organic C functional group, and in some cases, spectral data collection and processing influenced the quantification of organic C functional groups in a given biochar to the extent that the differences observed were as large as differences observed between biochars when analyzed using the same spectral data collection and processing technique. We conclude that great caution must be taken when comparing studies that determined organic C functional groups in materials using NMR-INTEG versus XANES-DECONV.

Automated summary

Solid-state C-13 Nuclear Magnetic Resonance (NMR) and synchrotron-based X-ray Absorption Near-Edge Structure (XANES) have applications for determining the relative proportions of organic C functional groups in materials. NMR had a better ability than XANES to differentiate % aromatic C across biochars, but the associations between NMR and XANES varied for different organic C functional groups.