Journal de chimie analytique environnementale

Structural characterization of Humic Materials Using 13C Nuclear Magnetic Resonance Techniques: A Comparison of Solution and Solid-State Methods

Abstract

Catherine FM Clewett, Todd M Alam, Eric S Osantowski and Michael J Pullin

The analysis of carbon type distribution and chemical structure of natural organic matter (NOM) by 13C NMR spectroscopy is important for understanding its origins and reactivity. While prior work has used solution-state NMR, solid-state NMR has the potential to provide this information with less instrument time and sample processing, while providing an array of advanced filtering techniques. Quantitative and qualitative analyses with 13C solid-state magic angle spinning (MAS) NMR techniques are described for three commercially available samples and one fulvic acid sample isolated from the Rio Grande in New Mexico. This study demonstrates the utility of solid-state 13C NMR for aquatic NOM structural characterization by determining the % carbon type for three standard natural organic materials and comparing these results to the existing solution-state 13C NMR determinations. The solid-state 13C MAS NMR results are used to determine % carbon distribution, estimates of elemental composition (%C, %H, %(O+N)), aromatic fraction (fa), nonprotonated aromatic fraction (faN), an estimate of aromatic cluster size, and ratio of sp2 to sp3 carbons. Additionally, Gaussian deconvolution is used for a more detailed analysis of carbon type than frequency band integration techniques. The solid-state 13C NMR results of these analyses indicate the chemical composition of Rio Grande fulvic acid has higher aromatic fraction and nonprotonated aromatic fraction (fa =0.32, faN = 0.21) and a lower sp2/sp3 fraction and cluster size (sp2/sp3 = 0.66, C = 6) compared to Suwannee River fulvic acid (fa = 0.18, faN = 0.10, sp2/sp3 = 0.82, C = 8).