Multimodal, microspectroscopic speciation of legacy phosphorus in two US mid‐Atlantic agricultural soils

Abstract To understand phosphorus (P) mobility in agricultural soils and its potential environmental risk, it is essential to directly measure solid phase P speciation. Often, bulk P K‐edge X‐ray absorption near edge structure (XANES) spectroscopy followed by linear combination fitting (LCF) is utilized to determine the solid P phases in soil. However, this method may limit results to only a few major phases. Additionally, XANES spectra for different P species may have very similar features, leading to an over‐ or underestimate of their contribution to LCF. Here, an improved P speciation by pairing multimodal microbeam‐X‐ray fluorescence (µ‐XRF) mapping coupled with µ‐XANES (microbeam‐X‐ray absorption near edge structure) analysis to directly speciate major and minor P phases on the micron scale is provided. We combined maps of both tender (P, sulfur, aluminum, and silicon) and hard energy (calcium, iron [Fe], and manganese) elements to evaluate the elemental co‐locations with P. To better account for uncertainty assigning XANES peaks to individual compounds, a more quantitative fingerprinting by “spectral feature analysis” was completed. With this analysis, an R ‐factor is reported for the fit. These results were compared to traditional LCF. Pre‐edge fitting results revealed the presence of a two‐component pre‐edge feature for phosphate adsorbed to ferrihydrite. Additionally, phytate co‐precipitated with ferrihydrite (Phytate‐Fe‐Cop) had a pre‐edge feature, indicating direct association with Fe. Lastly, a unique P species associated with manganese oxide was identified in the soil via multimodal mapping and µ‐XANES. These results allow for better prediction of P dissolution and mobility.