Characterization of Natural Organic Matter by Nuclear Magnetic Resonance Spectroscopy

Natural organic matter (NOM) is a major intermediate in the global carbon, nitrogen, sulfur, and phosphorus cycles. NOM is also the environmental matrix that frequently controls binding, transport, degradation, and toxicity of many organic and inorganic contaminants. Despite its importance, NOM is poorly understood at the structural chemistry level because of its molecular complexity and heterogeniety. Nuclear magnetic resonance (NMR) spectroscopy is one of the most useful spectrometric methods used to investigate NOM structure because qualitative and quantitative organic structure information for certain organic elements can be generated by NMR for NOM in both the solution and solid states under nondegradative conditions. However, NMR spectroscopy is not as sensitive as infrared or ultraviolet-visible spectroscopy; it is not at present applicable to organic oxygen and sulfur, and quantification of NMR spectra is difficult under certain conditions. The purpose of this overview is to present briefly the “state of the art” of NMR characterization of NOM, and to suggest future directions for NMR research into NOM. More comprehensive texts concerning the practice of NMR spectroscopy and its application to NOM in various environments have been produced by Wilson and by Wershaw and Mikita. Carbon, hydrogen, and oxygen are the major elements of NOM; together they comprise about 90% of the mass. The minor elements that constitute the remainder are nitrogen, sulfur, phosphorus, and trace amounts of the various halogen elements. With the exception of coal, in which carbon is the most abundant element, the order of relative abundance in NOM on an atomic basis is H > C > O > N > S > P = halogens. The optimum NMR-active nuclei for these elements are 1H, 13C, 17O, 15N, 33S, 31P, and 19F. The natural abundances and receptivities of these nuclei relative to 1H are given in Table 12.1. Quadrupolar effects for 17O, 33S, and halogen elements other than 19F lead to line broadening that greatly limits resolution in NMR studies of these elements in NOM.