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Soil organic phosphorus (P) is an important P source for biota especially in P-limited forests. Organic P has various chemical formations which differ in bioavailability and these organic P can be degraded by phosphatase enzymes. Here, we report soil P fractions inferred from solution 31P-NMR spectroscopy and soil phosphatase activities of two tropical rain forests on contrasting parent materials; sedimentary and ultramafic igneous (serpentinite) rocks. Compared to the sedimentary soils　and previous studies, P fractions of the serpentinite soils have distinctly high proportions of pyrophosphate and scyllo-inositol hexakisphosphate (scyllo-IP6). The accumulation of pyrophosphate and scyllo-IP6 may be related to strong sorptive capacity of iron oxides present in the serpentinite soils, which implies a consequent low P availability in the serpentinite soils. Mean value of soil phosphatase activities was higher in the serpentinite soils than in the sedimentary soils, suggesting that biota in these serpentinite forests depend more on soil organic P as a P source. [ABSTRACT FROM AUTHOR]