Structural characteristics of humic substances in buried ancient paddy soils as revealed by (13)C NMR spectroscopy

The study of organic matter in ancient paddy soils is helpful for understanding the influence of human activities on soil carbon sequestration and global climate change. However, little information on the spatial distribution and structural characteristics of the humic substances (HS) in ancient paddy soils is available. The spatial distributions of humic acids (HAs) and fulvic acids (FAs) in ancient paddy soils and modern cultivated paddy soils at the Shanlonggang site on the Liyang Plain were investigated, and the associated structures were characterized by using (13)C nuclear magnetic resonance (NMR). The (13)C NMR spectra revealed the following carbon types in HAs and FAs in both types of paddy soil in order of decreasing abundance: O-alkyl carbon (ranging from 39.7 to 51.8% and from 42.6 to 50.9%, respectively) ≥ alkyl carbon (ranging from 16.8 to 23.5% and from 15.7 to 22.4%, respectively) ≈ carboxyl carbon (ranging from 13.3 to 19.3% and from 16.9 to 22.0%, respectively) > aromatic carbon (ranging from 12.8 to 23.5% and from 10.0 to 17.2%, respectively). Moreover, the degree of aromaticity of HA was higher than that of FA in both soil samples. The humic constituents of the buried ancient paddy soils were less aromatic and oxidized than those of the modern cultivated paddy soils. The organic carbon in the ancient paddy soils was also less aromatic and oxidized than that in the modern cultivated paddy soils, suggesting that the structures of the HS in the ancient paddy soils were relatively simple. The results of this study provide new insights into the effect of secondary paddy soil formation on the spatial distribution, structural characteristics, and stability mechanisms of the HS in ancient paddy soils.