Distribution and speciation of arsenic around roots in a contaminated riparian floodplain soil: Micro-XRF element mapping and EXAFS spectroscopy

Riparian soils are periodically flooded, leading to temporarily reducing conditions. Diffusion of O₂ through plants into the rhizosphere maintains oxic conditions around roots, thereby promoting trace element fractionation along a redox gradient from the reduced soil matrix towards the oxic rhizosphere. The aim of this study was to determine the distribution and speciation of arsenic around plant roots in a contaminated (170-280 mg/kg As) riparian floodplain soil (gleyic Fluvisol). The analysis of soil thin sections by synchrotron micro-X-ray fluorescence (μ-XRF) spectrometry showed that As and Fe were enriched around roots and that As was closely correlated with Fe. Arsenic contents of three manually separated rhizosphere soil samples from the subsoil were 5-9 times higher than respective bulk As contents. This corresponds to the accumulation of about half of the total As in the subsoil in Fe-enrichments around roots. The speciation of As in the soil was assessed by oxalate extractions at pH 3.0 as well as by X-ray absorption near edge structure (XANES) and extended X-ray fine structure (EXAFS) spectroscopy. More than 77% of the total As was oxalate extractable in all samples. XANES and EXAFS spectra demonstrated that As was predominantly As(V). For the accurate analysis of the EXAFS data with respect to the bonding of As(V) to the Fe- or Al-octahedra of (hydr)oxides and clays, all 3-leg and 4-leg multiple scattering paths within the As^(V)O₄-tetrahedron were considered in a fully constrained fitting scheme. We found that As(V) was predominantly associated with Fe-(hydr)oxides, and that sorption to Al- and Mn-hydroxides was negligible. The accumulation of As in the rhizosphere may affect As uptake by plants. Regarding the mobility of As, our results suggest that by oxygenation of the rhizosphere, plants attenuate the leaching of As from riparian floodplain soils during periods of high groundwater levels or flooding.