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.
The potential to change agricultural land use to increase soil carbon stocks has been proposed as a mechanism to offset greenhouse gas emissions. To estimate the potential carbon storage in the soil from regional surveys it is important to understand the influence of environmental variables (climate, soil type, and landscape) before land management can be assessed. A survey was done of 354 sites to determine soil organic carbon stock (SOC stock; Mg C/ha) across the Lachlan and Macquarie catchments of New South Wales, Australia. The influences of climate, soil physical and chemical properties, landscape position, and 10 years of land management information were assessed. The environmental variables described most of the regional variation compared with management. The strongest influence on SOC stock at 0–10 cm was from climatic variables, particularly 30-year average annual rainfall. At a soil depth of 20–30 cm, the proportion of silica (SiO2) determined by mid-infrared spectra (SiMIR) had a negative relationship with SOC stock, and sand and clay measured by particle size analysis also showed strong relationships at sites where measured. Of the difference in SOC stock explained by land use, cropping had lower soil carbon than pasture in rotation or permanent pasture at 0–10 cm. This relationship was consistent across a rainfall gradient, but once soil carbon was standardised per mm of average annual rainfall, there was a greater difference between cropping and permanent pasture with increasing SiMIR in soils. Land use is also regulated by climate, topography, and soil type, and the effect on SOC stock is better assessed in smaller land-management units to remove some variability due to climate and soil.
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