N-CPMAS nuclear magnetic resonance spectroscopy and biological stability of soil organic nitrogen in whole soil and particle-size fractions

Abstract Soil organic nitrogen was quantified by solid-state 15 N cross-polarization nuclear magnetic resonance spectroscopy (NMR) during a 14-month laboratory incubation of a sandy loam soil amended with 15 N-clover. In whole soil and particle-size fractions, the clover-derived N was always 85-90% amide, 5-10% guanidinium N of arginine, and 5% amino. Quantitativeness of these results was suggested by (1) analysis of a standard containing a complex mixture of organic 15 N and (2) correlation of spectral intensities with 15 N concentrations. Based on the unchanging proteinaceous NMR signature of clover-derived N throughout the incubation, differences in the mineralization/immobilization kinetics of clover-N among the different particle-size fractions appeared not to be linked to organic functional group. Kinetic analysis of the mineralization of 15 N, with correction of rate constants for field temperatures, suggested that the proteinanceous 15 N in the clay and fine silt fractions observed here had a mean residence time of 7 years in the field.

Estimating the molecular composition of a diverse range of natural organic materials from solid-state 13C NMR and elemental analyses

Most techniques for determining the chemical nature of natural organic matter in soil, sediment and water require prior extraction or concentration steps that are not quantitative and that create artifacts. 13C nuclear magnetic resonance (NMR) analysis can avoid these problems, but it gives little information at the scale of molecules. Here we show that the molecular composition of a diverse range of natural organic materials could be inferred from 13C NMR analysis combined with C and N analysis. Forty-six different organic materials including undecomposed and decomposed plant materials, soil organic matter, phytoplankton, and the organic matter found in freshwater, estuarine and marine sediments were examined. A mixing model simultaneously solved a series of equations to estimate the content of four biomolecule components representing the organic materials produced in greatest abundance by plants and other organisms (carbohydrate, protein, lignin and aliphatic material) and two additional components (char and pure carbonyl). Based on defined molecular structures for each component, signal intensities for 13C NMR spectra were predicted and compared with measured values. The sum of the absolute differences in signal intensity between the measured and predicted spectral regions was <7% for the terrestrial materials. For aquatic materials the fit of the predicted to measured signal intensities was not as good. Predicted molecular compositions correlated well with independent analyses of cellulose, protein and lignin contents of plant samples and char contents of soil samples. Across all samples, carbohydrates accounted for 10-76% of the sample C (40-76% in plants and 10-42% in soils, sediments and phytoplankton), protein for 2-80% (21-80% in phytoplankton and marine water column samples and 2-36% in plants, soils and sediments), lignin for 0-36%, aliphatic materials for 2-44%, char for 0-38% and carbonyl for 0-22%. For the soils, sediments and decomposed plant materials, the close correspondence between actual signal intensities and those predicted using known biomolecular components, suggested that either ‘humic’ structures can be approximated by mixtures of common biologically derived molecules or that humic structures did not exist in significant amounts

Distribution and thermal stability of physically and chemically protected organic matter fractions in soils across different ecosystems

Accrual of carbon (C) and nitrogen (N) in soil is a significant and realizable management option to mitigate climate change; thus, a clear understanding of the mechanisms controlling the persistence of C and N in soil organic matter (SOM) across different ecosystems has never been more needed. Here, we investigated SOM distribution between physically and chemically stabilized fractions in soils from a variety of ecosystems (i.e., coniferous and broadleaved forest soils, grassland soils, technosols, and agricultural soils). Using elemental and thermal analyses, we examined changes in the quantity and quality of physically fractionated SOM pools characterized by different mechanisms of protection from decomposition. Independently of the ecosystem type, most of the organic C and total N were found in the mineral-associated SOM pool, known to be protected mainly by chemical mechanisms. Indexes of thermal stability and C/N ratio of this heavy SOM fraction were lower (especially in agricultural soils) compared to light SOM fractions found free or occluded in aggregates, and suggested a marked presence of inherently labile compounds. Our results confirm that the association of labile organic molecules with soil minerals is a major stabilization mechanism of SOM, and demonstrate that this is a generalizable finding occurring across different mineral soils and ecosystems