Uranium (VI) Adsorbate Structures on Portlandite [Ca(OH)2] Type Surfaces Determined by Computational Modelling and X-ray Absorption Spectroscopy

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

Soft X-ray Photochemistry at the L₂,₃-edges in K₃[Fe(CN)₆], [Co(acac)₃] and [Cp₂Fe][BF₄]

Soft X-ray photoreduction has been observed in K3[Fe(CN)6], [Co(acac)3] and [Cp2Fe][BF4]

Toxicokinetics of Ag in the terrestrial isopod Porcellionides pruinosus exposed to Ag NPs and AgNO3 via soil and food

Silver nanoparticles (Ag NPs) have been used in numerous consumer products and may enter the soil through the land application of biosolids. However, little is known about the relationship between Ag NP exposure and their bioavailability for soil organisms. This study aims at comparing the uptake and elimination kinetics of Ag upon exposures to different Ag forms (NPs and ionic Ag (as AgNO3)) in the isopod Porcellionides pruinosus. Isopods were exposed to contaminated Lufa 2.2 soil or alder leaves as food. Uptake and elimination rate constants for soil exposure did not significantly differ between Ag NPs and ionic Ag at 30 and 60 mg Ag/kg. For dietary exposure, the uptake rate constant was up to 5 times higher for Ag NPs than for AgNO3, but this was related to feeding activity and exposure concentrations, while no difference in the elimination rate constants was found. When comparing both routes, dietary exposure resulted in lower Ag uptake rate constants but elimination rate constants did not differ. A fast Ag uptake was observed from both routes and most of the Ag taken up seemed not to be eliminated. Synchrotron X-ray fluorescence showed Ag in the S-cells of the hepatopancreas, thus supporting the observations from the kinetic experiment (i.e. low elimination). In addition, our results show that isopods have an extremely high Ag accumulation capacity, suggesting the presence of an efficient Ag storage compartment

Uptake routes and toxicokinetics of silver nanoparticles and silver ions in the earthworm Lumbricus rubellus

Current bioavailability models, such as the free ion activity model and biotic ligand model, explicitly consider that metal exposure will be mainly to the dissolved metal in ionic form. With the rise of nanotechnology products and the increasing release of metal-based nanoparticles (NPs) to the environment, such models may increasingly be applied to support risk assessment. It is not immediately clear, however, whether the assumption of metal ion exposure will be relevant for NPs. Using an established approach of oral gluing, a toxicokinetics study was conducted to investigate the routes of silver nanoparticles (AgNPs) and Ag+ ion uptake in the soil-dwelling earthworm Lumbricus rubellus. The results indicated that a significant part of the Ag uptake in the earthworms is through oral/gut uptake for both Ag+ ions and NPs. Thus, sealing the mouth reduced Ag uptake by between 40% and 75%. An X-ray analysis of the internal distribution of Ag in transverse sections confirmed the presence of increased Ag concentrations in exposed earthworm tissues. For the AgNPs but not the Ag+ ions, high concentrations were associated with the gut wall, liver-like chloragogenous tissue, and nephridia, which suggest a pathway for AgNP uptake, detoxification, and excretion via these organs. Overall, the results indicate that Ag in the ionic and NP forms is assimilated and internally distributed in earthworms and that this uptake occurs predominantly via the gut epithelium and less so via the body wall. The importance of oral exposure questions the application of current metal bioavailability models, which implicitly consider that the dominant route of exposure is via the soil solution, for bioavailability assessment and modeling of metal-based NPs

Uranium (VI) Adsorbate Structures on Portlandite [Ca(OH) 2 ] Type Surfaces Determined by Computational Modelling and X-ray Absorption Spectroscopy

From MDPI via Jisc Publications RouterHistory: accepted 2021-11-03, pub-electronic 2021-11-08Publication status: PublishedFunder: Engineering and Physical Sciences Research Council; Grant(s): EP/1036389/1Portlandite [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

Provenance of uranium particulate contained within Fukushima Daiichi Nuclear Power Plant Unit 1 ejecta material.

Here we report the results of multiple analytical techniques on sub-mm particulate material derived from Unit 1 of the Fukushima Daiichi Nuclear Power Plant to provide a better understanding of the events that occurred and the environmental legacy. Through combined x-ray fluorescence and absorption contrast micro-focused x-ray tomography, entrapped U particulate are observed to exist around the exterior circumference of the highly porous Si-based particle. Further synchrotron radiation analysis of a number of these entrapped particles shows them to exist as UO2-identical to reactor fuel, with confirmation of their nuclear origin shown via mass spectrometry analysis. While unlikely to represent an environmental or health hazard, such assertions would likely change should break-up of the Si-containing bulk particle occur. However, more important to the long-term decommissioning of the reactors at the FDNPP (and environmental clean-upon), is the knowledge that core integrity of reactor Unit 1 was compromised with nuclear material existing outside of the reactors primary containment

The limitations of hibonite as a single-mineral oxybarometer for early solar system processes

The relationships between the composition of hibonite with the general formula CaAl12-2x-yMgxTi4 +xTi3 +yO19, the oxidation state of Ti (Ti3 +/ΣTi, where ΣTi = Ti3 + + Ti4 +), and oxygen fugacity (fO2) were investigated experimentally. It was found that hibonite can be synthesised with a range of Ti3 +/ΣTi values at constant fO2 and with a constant Ti3 +/ΣTi value for a range of fO2s. It was also found that if hibonite with the formula CaAl12-yTi3 +yO19 (Ti3 +/ΣTi = 1) is equilibrated with a melt of CAI composition at fO2s below the iron-wüstite buffer then the resulting hibonite contained Mg, with Mg per formula unit (pfu) ~ 0.8 Ti pfu, and Ti3 +/ΣTi ~ 0.2, irrespective of the fO2. These results suggest that the availability of Mg, rather than fO2, is the key factor that determines Ti3 +/ΣTi of hibonite. The structures of synthetic samples of hibonite with the general formula CaAl12-2xMgxTi4 +xO19, where 0 ≤ X < 1, were determined by Rietveld refinement of X-ray powder diffraction data. The predominant site occupied by Ti4 + was found to change from M2 to M4 with increasing Ti content. The range of Ti concentrations over which the site occupancy changed corresponds to that observed in meteoritic hibonite. This change in the Ti4 + site produces changes in the Ti K-edge XANES spectra, particularly in the intensity of the pre-edge feature, for constant Ti3 +/ΣTi. The observed dependence of the pre-edge on the Ti4 + site was reproduced by ab initio simulations of the XANES spectra. The XANES spectra of natural hibonite with variable Ti content from the Murchison carbonaceous chondrite closely match the spectra of the synthetic samples with similar Ti contents. These differences in the spectra of meteoritic hibonite could be misinterpreted as being due to changes in Ti3 +/ΣTi, but are instead due to differences in ΣTi, which relate to the petrogenetic history. Crystal chemistry exerts a first order control on the Ti site occupancy and Ti3 +/ΣTi value of hibonite. As a result, no simple relationship between Ti3 +/ΣTi and fO2 should be expected. It is unlikely that hibonite will be useful as an oxybarometer for solar processes without Ti3 +/ΣTi standards that are compositionally matched to the unknown

Chemical tomography data

XRD-CT and XRF-CT data sets associated with publication "Chemical Imaging of Fischer Tropsch Catalysts Under Operating Conditions". Numbered files contain raw XRF and absorption data as collected along with the meta data. Non-numbered files contain processed and azimuthally integrated XRD data. The XRD calibration file has also been included

Microbial endolithic colonization and the geochemical environment in young seafloor basalts

The colonization and weathering of young seafloor basaltic glass from the mid-Atlantic Ridge was examined. Microorganisms were localised to fractures in the surface of the basalt and grew on the surfaces of material in the fractures. XAS. Raman spectroscopy and NanoSIMS analysis of the fracture-filling material shows that it contains non-crystallised iron-enriched altered glass and poorly ordered iron oxides. Organisms, which in places develop into contiguous biofilms, develop on the surface of the material. No putative biogenic alteration textures were observed in the basaltic glass at the fracture boundaries suggesting that the microbial community is restricted to the secondary alteration products. Microbial culturing shows the presence of heterotrophic bacteria including Sufitobacter and Halomonas consistent with observations of photic zone detritus associated with fracture-filling material. These data show that the interior of fresh basaltic glass is an endolithic habitat for microorganisms, but that the glass itself is not a primary source of cations or energy for the developing communities