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Abstract: Portlandite [Ca(OH)2] is a potentially dominant solid phase in the high pH fluids expected within the cementitious engineered barriers of Geological Disposal Facilities (GDF). This study combined X-ray Absorption Spectroscopy with computational modelling in order to provide atomic-scale data which improves our understanding of how a critically important radionuclide (U) will be adsorbed onto this phase under conditions relevant to a GDF environment. Such data are fundamental for predicting radionuclide mass transfer. Surface coordination chemistry and speciation of uranium with portlandite [Ca(OH)2] under alkaline groundwater conditions (ca. pH 12) were determined by both in situ and ex situ grazing incidence extended X-ray absorption fine structure analysis (EXAFS) and by computational modelling at the atomic level. Free energies of sorption of aqueous uranyl hydroxides, [UO2(OH)n]2–n (n = 0–5) with the (001), (100) and (203) or (101) surfaces of portlandite are predicted from the potential of mean force using classical molecular umbrella sampling simulation methods and the structural interactions are further explored using fully periodic density functional theory computations. Although uranyl is predicted to only weakly adsorb to the (001) and (100) clean surfaces, there should be significantly stronger interactions with the (203/101) surface or at hydroxyl vacancies, both prevalent under groundwater conditions. The uranyl surface complex is typically found to include four equatorially coordinated hydroxyl ligands, forming an inner-sphere sorbate by direct interaction of a uranyl oxygen with surface calcium ions in both the (001) and (203/101) cases. In contrast, on the (100) surface, uranyl is sorbed with its axis more parallel to the surface plane. The EXAFS data are largely consistent with a surface structural layer or film similar to calcium uranate, but also show distinct uranyl characteristics, with the uranyl ion exhibiting the classic dioxygenyl oxygens at 1.8 Å and between four and five equatorial oxygen atoms at distances between 2.28 and 2.35 Å from the central U absorber. These experimental data are wholly consistent with the adsorbate configuration predicted by the computational models. These findings suggest that, under the strongly alkaline conditions of a cementitious backfill engineered barrier, there would be significant uptake of uranyl by portlandite to inhibit the mobility of U(VI) from the near field of a geological disposal facility.

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Abstract: Neptunium and uranium are important radionuclides in many aspects of the nuclear fuel cycle and are often present in radioactive wastes which require long term management. Understanding the environmental behaviour and mobility of these actinides is essential in underpinning remediation strategies and safety assessments for wastes containing these radionuclides. By combining state-of-the-art X-ray techniques (synchrotron-based Grazing Incidence XAS, and XPS) with wet chemistry techniques (ICP-MS, liquid scintillation counting and UV-Vis spectroscopy), we determined that contrary to uranium(VI), neptunium(V) interaction with magnetite is not significantly affected by the presence of bicarbonate. Uranium interactions with a magnetite surface resulted in XAS and XPS signals dominated by surface complexes of U(VI), while neptunium on the surface of magnetite was dominated by Np(IV) species. UV-Vis spectroscopy on the aqueous Np(V) species before and after interaction with magnetite showed different speciation due to the presence of carbonate. Interestingly, in the presence of bicarbonate after equilibration with magnetite, an unknown aqueous NpO2+ species was detected using UV-Vis spectroscopy, which we postulate is a ternary complex of Np(V) with carbonate and (likely) an iron species. Regardless, the Np speciation in the aqueous phase (Np(V)) and on the magnetite (111) surfaces (Np(IV)) indicate that with and without bicarbonate the interaction of Np(V) with magnetite proceeds via a surface mediated reduction mechanism. Overall, the results presented highlight the differences between uranium and neptunium interaction with magnetite, and reaffirm the potential importance of bicarbonate present in the aqueous phase.

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Abstract: Trace element inventories are known to correlate with specific histological structures in bone, reflecting organismal physiology and life histories. By studying trace elements in fossilised bone, particularly in individuals with cyclic bone growth (alternating fast/slow bone deposition), we can improve our understanding of the physiology of extinct organisms. In this study we present the first direct comparison between optical histology (bone tissue identification) and synchrotron-based chemical mapping, quantification, and characterisation of trace elements (biochemistry) within cyclic growth tissues, in this case within bones of a cave hyaena (Crocuta crocuta spelaea). Results show distributions of zinc, an element strongly associated with active ossification and bone growth, correlating with (1) fast-growing tissue of zonal bone (cyclic growth) in an extinct hyaena and (2) secondary osteons (remodelling) in both extant and extinct hyaena. Concentrations and coordination chemistry of zinc within the fossil sample are comparable to those seen in extant bone suggesting that zinc is endogenous to the sample and that the chemistry of bone growth has been preserved for 40 ka. These results demonstrate that the study of trace elements as part of the histochemistry has wide utility for reconstructing growth, diet and other lifestyle factors in archaeological and fossil bone.

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Abstract: Fossils of juvenile Mesozoic birds provide insight into the early evolution of avian development, however such fossils are rare. The analysis of the ossification sequence in these early-branching birds has the potential to address important questions about their comparative developmental biology and to help understand their morphological evolution and ecological differentiation. Here we report on an early juvenile enantiornithine specimen from the Early Cretaceous of Europe, which sheds new light on the osteogenesis in this most species-rich clade of Mesozoic birds. Consisting of a nearly complete skeleton, it is amongst the smallest known Mesozoic avian fossils representing post-hatching stages of development. Comparisons between this new specimen and other known early juvenile enantiornithines support a clade-wide asynchronous pattern of osteogenesis in the sternum and the vertebral column, and strongly indicate that the hatchlings of these phylogenetically basal birds varied greatly in size and tempo of skeletal maturation.

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Abstract: The hindlimb of theropod dinosaurs changed appreciably in the lineage leading to extant birds, becoming more ‘crouched’ in association with changes to body shape and gait dynamics. This postural evolution included anatomical changes of the foot and ankle, altering the moment arms and control of the muscles that manipulated the tarsometatarsus and digits, but the timing of these changes is unknown. Here, we report cellular-level preservation of tendon- and cartilage-like tissues from the lower hindlimb of Early Cretaceous Confuciusornis. The digital flexor tendons passed through cartilages, cartilaginous cristae and ridges on the plantar side of the distal tibiotarsus and proximal tarsometatarsus, as in extant birds. In particular, fibrocartilaginous and cartilaginous structures on the plantar surface of the ankle joint of Confuciusornis may indicate a more crouched hindlimb posture. Recognition of these specialized soft tissues in Confuciusornis is enabled by our combination of imaging and chemical analyses applied to an exceptionally preserved fossil.