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Understanding the effects of a fertilization regime on the long-term accumulation and transformation of soil phosphorus (P) is essential for promoting the development of sustainable management of soil P. Based on a 29-year field experiment in Mollisol, the compositions and changes of P forms using a modified Hedley sequential extraction method, solution 31P-NMR and P K-edge XANES and soil properties were investigated under continuous mono maize with and without manure (NPKM and NPK). Results showed a stronger positive related coefficient between soil total P and labile P, and mid-labile P fraction was found in NPKM than in NPK treatment. It indicated NPKM could improve the availability of soil accumulated P and reduce its transformation to stable P. Accumulated inorganic P (Pi) was dominated by aluminum phosphate (Al-P) and monobasic calcium phosphate monohydrate (MCP) for NPK treatment, Al-P, MCP, and tricalcium phosphate for NPKM treatment with XANES analysis, which contributed to the P availability in Mollisol. Moreover, the proportion of IHP with XANES and ratio of orthophosphate diesters to monoesters in NPK compared to NPKM indicated the higher Po lability with NPK treatment. Pi, especially NaHCO3-Pi and NaOH-Pi, were the potential sources of resin-Pi. Soil organic matter (SOM), organic-bound iron, and alumina oxide (Fep + Alp) showed significant influence on the transformation of P forms. Our research suggested that due to the rise in SOM and Fep + Alp, the fertilization regime significantly increased most highly active soil P fractions, especially in NPKM treatment. This work gives new insight into sustainable P management, which benefits the reduction in soil P accumulation. [ABSTRACT FROM AUTHOR]