Elucidation of soil phosphorus speciation in mid-Atlantic soils using synchrotron-based microspectroscopic techniques

Phosphorus deficiency and excess are concomitant problems in agricultural soils of the mid-Atlantic region. A fundamental understanding of soil P speciation is essential to assess P fate and transport in these soils. Current methods for soil P speciation often rely on sequential chemical extractions, which can introduce artifacts during analysis. To overcome limitations of current methods, this study evaluated synchrotron-based micro-focused X-ray fluorescence (µ-XRF) and X-ray absorption near-edge spectroscopy (µ-XANES) techniques to assess soil P speciation in agricultural soils collected from the mid-Atlantic region of the United States. Three soils with varying chemical and physical properties were analyzed with µ-XRF maps collected at high (12,000 eV) and tender (2240 eV) energies to evaluate colocation of P with Fe, Al, Ca, and Si in soil samples, and µ-XANES spectra were collected at the P K-edge for P hotspots. Combined µ-XRF and µ-XANES analysis was useful for identifying Ca phosphate, Fe phosphate, Al-sorbed P, and Fe-sorbed P species in heterogeneous soil samples. X-ray fluorescence maps were valuable to distinguish Al-oxide sorbed P from Fe-oxide sorbed P species. A low signal-to-noise ratio often limited µ-XANES data collection in regions with diffuse, low concentrations of P. Therefore, some P species may not have been detected during analysis. Even with varying degrees of self-absorption and signal-to-noise ratios in µ-XANES spectra, important inferences regarding P speciation in mid-Atlantic soils were made. This study highlights the potential of µ-XANES analysis for use in environmental and agricultural sciences to provide insights into P fate and transport in soils.