Calcium phosphate (CaP) minerals may comprise the main phosphorus (P) reserve in alkaline soils, with solubility dependent on pH and the concentration of Ca and/or P in solution. Combining several techniques in a novel way, we studied these phenomena by progressively depleting P from suspensions of two soils (low P) using an anion-exchange membrane (AEM) and from a third soil (high P) with AEM together with a cation-exchange membrane. Depletions commenced on untreated soil, then continued as pH was manipulated and maintained at three constant pH levels: the initial pH (pHi) and pH 6.5 and 5.5. Bulk P K-edge X-ray absorption near-edge structure (XANES) spectroscopy revealed that the main forms of inorganic P in each soil were apatite, a second more soluble CaP mineral, and smectite-sorbed P. With moderate depletion of P at pHi or pH 6.5, CaP minerals became more prominent in the spectra compared to sorbed species. The more soluble CaP minerals were depleted at pH 6.5, and all CaP minerals were exhausted at pH 5.5, showing that the CaP species present in these alkaline soils are soluble with decreases of pH in the range achievable by rhizosphere acidification.

Alkaline Vertisols contain calcium phosphate (CaP) minerals that dissolve in response to both acidification and the depletion of concentration of phosphorus (P) or calcium (Ca) in the soil solution, conditions commonly observed within the rhizosphere. In these soils, reserve-P is defined as the difference between the concentrations of P extracted by 0.5M sodiumbicarbonate and 0.005M sulfuric acid. Tomimic rhizosphere modification we sequentially extracted P from three alkaline Vertisols that contained concentrations of reserve-P ranging from 300 to 6500 mg kg⁻¹ using an anion sink, and a combined anion and cation sink. The extractions commenced on untreated soil, and then three target pH regimes were imposed: 1) maintain the initial pH; 2) incrementally acidify to pH 6.5 then maintain; and 3) incrementally acidify to pH 5.5 then maintain. Extractable P increased with decreasing solution pH in all soils until the acid soluble P was depleted. In each soil and at each pH level,more P was extracted when the combined sink was used compared with the anion sink alone. The release of acid soluble-P in these soils was indicative of CaP minerals of varying thermodynamic stability. In addition to the relatively constant concentrations of P extracted at the initial pH with the anion sink, moderate acidification to pH 6.5 released 9% of the reserve-P in the high P soil, but this varied from 18 to 33% in the two other soils containing lower soil P. These findings show that the release of P in alkaline soils beyond that measured by a bicarbonate extractant is influenced by the modification of soil pH and by the removal of Ca from the solution, which has implications for plant availability and response to added fertiliser. Further research is needed to identify the individual species of soil P that are involved in buffering the soil solution, and what their potential availability is to plants via rhizosphere modification.

Acid-soluble soil phosphorus (P) is a potential resource in P-limited agricultural systems that may become critical as global P sources decrease in the future. The fate of P in three alkaline Vertisols, a major agricultural soil type, after acidic incubation was investigated using synchrotron-based K-edge X-ray absorption near-edge structure (XANES) spectroscopy, geochemical modeling, wet chemistry soil extraction, and a P sorption index. Increases in labile P generally coincided with decreased stability and dissolution of calcium phosphate (CaP) minerals. However, only a minor proportion of the CaP dissolved in each soil was labile. In two moderate-P soils (800 mg P kg^–1), XANES indicated that approximately 160 mg kg^–1 was repartitioned to sorbed phases at pH 5.1 of one soil and at pH 4.4 of the second; however, only 40 and 28% were labile, respectively. In a high-P soil (8900 mg P kg^–1), XANES indicated a decrease in P of 1170 mg kg^–1 from CaP minerals at pH 3.8, of which approximately only 33% was labile. Phosphorus mobilized by agricultural practices without concurrent uptake by plants may be repartitioned to sorbed forms that are not as plant-available as prior to acidification.

Phosphorus (P) available to plants in alkaline, vertic soils is thought to be buffered by the dissolution of various calcium phosphate minerals (CaP), driven by pH and the concentration of Ca and/or P in solution. To investigate this hypothesis we incrementally acidified 6 alkaline vertic soils of CaP 300-6000 mg kg⁻¹ in the presence or absence of an anion exchange P sink. Following the early removal of solution and sorbed P sources, P recovery remained low until soil pH passed key thresholds. These thresholds varied little between soils and with the sink (pH 6.0-6.3), and soil pH buffer capacity affected the amount of acid required to approach the thresholds. Dissolution of CaP species occurred 0.7-1.0 pH units higher where the solution P concentration was kept below 1 μM using the anion exchange membrane sink compared to acidification without the sink. The data support the hypothesis that rhizosphere acidification may increase the availability of CaP minerals to plants; however, the dependence of P release dynamics on pH buffering capacity may put P release beyond the reach of some plant species. Consequently, research is necessary to quantify both plant acidification potential in these soils and the effect of concomitant removal of Ca on release of CaP species into plant available forms.

Phosphorus (P) is an essential element for all life, serving as a structural component of cells, being integral in energy transfer, and a component of genes and enzymes (Campbell and Reece, 2002; Schachtman et al., 1998). More than other nutrients, P is held tightly by the soil, so only low concentrations relative to plant requirements are in the soil solution (Holford, 1997). In alkaline soils, it is generally accepted that P is retained in the soil as calcium phosphate (CaP) minerals, limiting plant growth and agricultural production (Conyers and Moody, 2009; Holford, 1997). This research investigates factors that influence the supply of P to the soil solution of alkaline Vertosols, focusing on pH and the concentration of P itself and calcium (Ca) in the solution. The soils were taken from the Northern Grains Region (NGR), a productive agricultural region of 4 M ha in northern New South Wales and southern Queensland, Australia. The soils contain a diminishing pool of phosphorus (P) that is rapidly available to plants, and an acid-soluble P fraction that has been considered to slowly replenish the available pool. The process of replenishment is not well understood, and this may lead to inefficient use of fertiliser P. It is possible that modification of soil in the rhizosphere, particularly acidification, enables plants to directly access the acid-soluble P fraction.