Mechanisms of phosphorus solubilisation in a limed soil as a function of pH

Phosphorus (P) quantity-intensity relationships are central to the solubility and release of P from soil to water. Relationships between P extractable by 0.5 M NaHCO extractable P (Olsen P; quantity, Q) and P extractable by 0.01 M CaCl(2) (CaCl(2)-P; possible predictor of soil solution or drainage water P; intensity, I) are curvilinear: above a certain Olsen P concentration, CaCl(2)-P becomes much more soluble than when below it. Aluminium-, Fe- and Ca-P forms (extractable by Olsen's reagent) are thought to control P solubility. Thus, our objectives were to identify P forms in equilibrium with CaCl(2)-P via solubility equilibrium experiments, and the behaviour of CaCl(2)-P in relation to Al, Fe and Ca associated P, determined with 31P high power decoupling magic angle spinning nuclear magnetic resonance spectroscopy (31P HPDec/MAS NMR). Results indicated that two Q-I relationships occurred, one for soils above pH 5.8, and the other for soils below pH 5.8. Above pH 5.8, soils were saturated with respect to hydroxyapatite (Ca(5)(PO(4))(3)OH) and undersaturated with respect to beta-tricalcium phosphate (beta-Ca(3)(PO(4))(2)), while log ion-activity products showed that all soils and pHs were either saturated or in equilibrium with variscite (AlPO(4).2H(2)O) or its amorphous analogue. Using 31P HPDec/MAS NMR, Ca-P was best correlated with CaCl(2)-P in soils above pH 5.8, and with Al-P in soils below this pH. This study demonstrates the value of solid-state NMR in conjunction with wet chemical techniques for the study of labile P and P loss from pasture soils with a wide range of managements.