Tetra- and hexavalent uranium forms bidentate-mononuclear complexes with particulate organic matter in a naturally uranium-enriched peatland

Peatlands frequently serve as efficient biogeochemical traps for U. Mechanisms of U immobilization in these organic matter-dominated environments may encompass the precipitation of U-bearing mineral(oid)s and the complexation of U by a vast range of (in)organic surfaces. The objective of this work was to investigate the spatial distribution and molecular binding mechanisms of U in soils of an alpine minerotrophic peatland (pH 4.7–6.6, Eh = −127 to 463 mV) using microfocused X-ray fluorescence spectrometry and bulk and microfocused U L3-edge X-ray absorption spectroscopy. The soils contained 2.3–47.4 wt % organic C, 4.1–58.6 g/kg Fe, and up to 335 mg/kg geogenic U. Uranium was found to be heterogeneously distributed at the micrometer scale and enriched as both U(IV) and U(VI) on fibrous and woody plant debris (48 ± 10% U(IV), x ± σ, n = 22). Bulk U X-ray absorption near edge structure (XANES) spectroscopy revealed that in all samples U(IV) comprised 35–68% of total U (x = 50%, n = 15). Shell-fit analyses...