Distribution and Speciation of Nutrient Elements around Micropores

In Australia a class of soils known as duplex soils covers approximately 20% of the continent. Their defining characteristic is a sharp texture contrast between the A (or E) and B horizon. The upper B horizon at the point of contact with the E horizon is often highly sodic and of such a high strength that root growth and proliferation, water conductivity, aeration, water storage, and water uptake are restricted. Roots growing in these soils rely on channels created by previous roots or cracks arising from shrink–swell forces associated with seasonal wetting and drying. Although the characteristics of rhizospheres compared with the soil matrix are well documented there is a paucity of knowledge about how long these changes persist after roots decay. This knowledge is fundamental to our understanding of root growth in duplex soils in which plants rely on pore networks formed by previous plants to proliferate in the subsoil. In this study we investigated the heterogeneous chemistry of micropores in situ using synchrotron-based μ-x-ray fluorescence spectroscopy (XRF), μ-x-ray absorption near edge structure spectroscopy (XANES), and extended μ-x-ray absorption fine structure spectroscopy (EXAFS). The distribution maps of Ca, Mn, Fe, Cu, and Zn at micrometer resolution were collected using μ-XRF. Subsequently, specific locations with higher concentrations (hot spots) of Mn, Fe, Cu, or Zn were selected and XANES and EXAFS spectra were collected to study the speciation of these elements around the micropore compared with the soil matrix. The μ-XRF maps showed that Mn was depleted around one of the micropores studied but accumulated around another micropore. Copper and Zn accumulated around the micropores, whereas Ca was predominantly inside micropores. There was no difference between matrix and micropore surface with respect to the distribution of Fe. Around micropores Mn was present in reduced form (Mn II) and Fe was in its oxidized form (Fe III). Manganese and Cu were present in the form of phosphates, Fe as Fe oxides, and Zn as Zn phosphates and adsorbed Zn.