Effects of chemical fertilizers and organic manure on the soil organic carbon (SOC) content in particle size fractions of paddy soil were investigated in a 17-year long-term fertilization field experiment in Zhejiang Province, China. The inherent chemical composition of silt- and clay-associated SOC was evaluated with solid-state 13C-NMR spectroscopy. Compared to CK (no fertilizer treatment), NPKRS (NPK fertilizers plus rice straw) , NPKOM (NPK fertilizers plus organic manure) , NPK (NPK fertilizers) and OM (organic manure alone) treatments significantly (P <0. 05) increased the SOC content of sand- (2-0.02 mm), silt- (0.02-0.002 mm) and clay-sized (< 0.002 mm) fractions. However, no significant difference was observed in the accumulation of silt- and clay-associated SOC between CK and rice straw (RS) treatments. Besides, in comparison with plots applied with NPK fertilizers alone, combined application of organic amendments and NPK fertilizers facilitated the storage of newly sequestered SOC in silt- and clay-sized fractions, which could be more conducive to the stability of SOC. Based on 13C-NMR spectra, both silt and clay fractions were composed of Alkyl-C, O-alkyl-C, Aromatic-C and carbonyl-C. Changes in the relative proportion of different C species were observed between silt and clay fractions: the clay fraction had relatively more Alkyl-C, carbonyl-C and less O-alkyl-C, Aromatic-C than those in the silt fraction. This might be ascribed to the fact that the organic matter complexed with clay was dominated by microbial products, whereas the silt appeared to be rich in aromatic residues derived from plants. The spectra also showed that the relative proportion of different C species was modified by fertilization practices. In comparison with organic amendments alone, the relative proportion of Alkyl-C was decreased by 9.1%-11.9% and 13.7%-19.9% under combined application of organic amendments and chemical fertilizers, for silt and clay, respectively, and that of O-alkyl-C was increased by 2.9%-6.3% and 13.4%-22.1%, respectively. These results indicated that NPKOM and NPKRS treatments reduced the decomposition rate of SOC. The aromaticity, hydrophobicity and, hence, chemical recalcitrance of silt- and clay-associated SOC in the NPK fertilizer treatments were lower than those of the organically amended plots and unfertilized treatments, indicating decreased recalcitrance of SOC against decomposition. We concluded that long-term application of organic manure combined with chemical fertilizers, either through increased accumulation of both recalcitrant compounds and carbohydrates or reduced decomposition of organic matter, was a sustainable strategy for facilitating carbon accumulation of the paddy soil investigated in this study.

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