Wetlands have been proposed to naturally attenuate U transfers in the environment via U complexation by organic matter and potential U reduction. However, U mobility may depend on the identity of particulate/dissolved uranium source materials and their redox sensitivity. Here, we examined the fate of uranium in a highly contaminated wetland (up to 4500 mg•kg −1 U) impacted by former mine water discharges. Bulk U L III -EXAFS and (micro-)XANES combined with SEM-EDXS analyses of undisturbed soil cores show a sharp U redox boundary at the water table, together with a major U redistribution from U(IV)-minerals to U(VI)-organic matter complexes. Above the water table, U is fully oxidized into mono-and bidentate U(VI)-carboxyl and monodentate U(VI)phosphoryl complexes. Minute amounts of U(VI)-phosphate minerals are also observed. Below the water table, U is fully reduced and is partitioned between U(IV)-phosphate minerals (i.e., ningyoite and a lermontovite-like phase), and bidentate U(IV)-phosphoryl and monodentate U(IV)-carboxyl complexes. Such a U redistribution from U-minerals inherited from mine water discharge deposits could result from redox cycling nearby the water table fluctuation zone. Oxidative dissolution of U(IV)-phosphate minerals could have led to U(VI)-organic matter complexation, followed by subsequent reduction into U(IV)-organic complexes. However, uranium(IV) minerals could have been preserved in permanently waterlogged soil.

The long-term fate of uranium-contaminated sediments, especially downstream former mining areas, is a widespread environmental challenge. Essential for their management is the proper understanding of uranium (U) immobilization mechanisms in reducing environments. In particular, the long-term behavior of noncrystalline U(IV) species and their possible evolution to more stable phases in subsurface conditions is poorly documented, which limits our ability to predict U long-term geochemical reactivity. Here, we report direct evidence for the evolution of U speciation over 3,300 y in naturally highly U-enriched sediments (350–760 µg ⋅ g−1 U) from Lake Nègre (Mercantour Massif, Mediterranean Alps, France) by combining U isotopic data (δ238U and (234U/238U)) with U L3-edge X-ray absorption fine structure spectroscopy. Constant isotopic ratios over the entire sediment core indicate stable U sources and accumulation modes, allowing for determination of the impact of aging on U speciation. We demonstrate that, after sediment deposition, mononuclear U(IV) species associated with organic matter transformed into authigenic polymeric U(IV)–silica species that might have partially converted to a nanocrystalline coffinite (UIVSiO4·nH2O)-like phase. This diagenetic transformation occurred in less than 700 y and is consistent with the high silica availability of sediments in which diatoms are abundant. It also yields consistency with laboratory studies that proposed the formation of colloidal polynuclear U(IV)–silica species, as precursors for coffinite formation. However, the incomplete transformation observed here only slightly reduces the potential lability of U, which could have important implications to evaluate the long-term management of U-contaminated sediments and, by extension, of U-bearing wastes in silica-rich subsurface environments.

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To cite this version:Jean-Claude Plaziat, J.L. Reyss, Abdelmajid Choukri, Charlotte Cazala. Diagenetic rejuvenation of raised coral reefs and precision of dating. The contribution of the Red Sea reefs to the question of reliability of the Uranium-series datings of middle to late Pleistocene key reef-terraces of the world. Carnets de Geologie, Carnets de Geologie, 2008, CG2008 (A04), pp.1-35. Abstract: This paper is a general review of the dating of reefs on the coasts of the Red Sea, including those of Egypt, Jordan, Sudan, Eritrea, Saudi Arabia and Djibouti. New methods of sampling and dating (U/Th) already tested on the reefs and associate deposits of the African coast of Egypt have demonstrated that processes of rejuvenation shown to exist in the best-preserved corals are probably attributable to the diagenesis of the organic material in their bio-minerals, thus justifying a revision of a great many datings of corals supposedly younger or older than the age assigned to the high-level isotopic substage (δ 18 O) MIS 5.5 (= 5e). During this late Pleistocene substage, a rapid lowering of sea level, short and limited to about ten meters, was detected and associated with a glacio-eustatic episode of global influence. A comparison of these Middle East reef chronologies with those of New Guinea, Australia and the western Atlantic that are referred only with difficulty to the δ 18 O global sea-level curves, casts doubt on the reliability of many regional reconstructions. Moreover the most "classic" reef chronologies, more or less out-of-phase with global isotopic records calls for a reexamination of the chronologic basis of the reference curves derived from marine isotopic data.Key Words: Th/U α dating; coral reef; Pleistocene; Red Sea; diagenesis; glaciation; sea-level change; rejuvenation hypothesis; Australia; Bahamas; Barbados; Bermudes; Djibouti; Egypt; Eritrea; Ethiopia; Jordan; Papua New Guinea; Sudan.

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