Macro- and micro-scale studies on U(VI) immobilization in hardened cement paste

Wet chemistry and synchrotron-based (micro-)spectroscopic investigations have been carried out to determine the uptake and speciation of U(VI) in hardened cement paste (HCP). The wet chemistry experiments included kinetic studies and the determination of the sorption isotherm. The latter measurements allowed conditions for linear sorption to be distinguished from those where precipitation occurred. Micro-X-ray fluorescence and X-ray absorption spectroscopy (μ-XRF/XAS) were used to determine the elemental distribution and the coordination environment of U(VI) in an intact HCP sample at the atomic level. The sample was prepared by in-diffusion of U(VI) into HCP over 9months. Micro-XRF maps revealed a heterogeneous distribution of U(VI) in a ten micron thick layer on the surface of the HCP disk. Micro-XAS measurements on a U(VI) hot spot showed that the coordination environment of U(VI) is similar to that in U(VI) doped HCP and in C-S-H sorption samples. To the best of our knowledge this is the first synchrotron-based micro-spectroscopic study on the speciation of diffusing uranyl ions with micro-scale spatial resolutio

Symmetry Analysis of Second Harmonic Generation at Surfaces of Antiferromagnets

Using group theory we classify the nonlinear magneto-optical response at low-index surfaces of fcc antiferromagnets, such as NiO. Structures consisting of one atomic layer are discussed in detail. We find that optical second harmonic generation is sensitive to surface antiferromagnetism in many cases. We discuss the influence of a second type of magnetic atoms, and also of a possible oxygen sublattice distortion on the output signal. Finally, our symmetry analysis yields the possibility of antiferromagnetic surface domain imaging even in the presence of magnetic unit-cell doubling.Comment: 23 pages, 10 figures incorporated. Accepted to Phys. Rev. B, scheduled for July'9

Nonlinear Magneto-Optics of Fe Monolayers from first principles: Structural dependence and spin-orbit coupling strength

We calculate the nonlinear magneto-optical response of free-standing fcc (001), (110) and (111) oriented Fe monolayers. The bandstructures are determined from first principles using a full-potential LAPW method with the additional implementation of spin-orbit coupling. The variation of the spin-orbit coupling strength and the nonlinear magneto-optical spectra upon layer orientation are investigated. We find characteristic differences which indicate an enhanced sensitivity of nonlinear magneto-optics to surface orientation and variation of the in-plane lattice constants. In particular the crossover from onedimensional stripe structures to twodimensional films of (111) layers exhibits a clean signature in the nonlinear Kerr-spectra and demonstrates the versatility of nonlinear magneto-optics as a tool for in situ thin-film analysis.Comment: 28 pages, RevTeX, psfig, submitted to PR

Application of micro X-ray diffraction to investigate the reaction products formed by the alkali–silica reaction in concrete structures

Alkali-silica reaction (ASR) is one of the most important deterioration mechanisms in concrete leading to substantial damages of structures worldwide. Synchrotron-based micro-X-ray diffraction (micro-XRD) was employed to characterize the mineral phases formed in micro-cracks of concrete aggregates as a consequence of ASR. This high spatial resolution technique enables to directly gain structural information on ASR products formed in a 40-year old motorway bridge damaged due to ASR. Micro-X-ray-fluorescence was applied on thin sections to locate the reaction products formed in veins within concrete aggregates. Micro-XRD pattern were collected at selected points of interest along a vein by rotating the sample. Rietveld refinement determined the structure of the ASR product consisting of a new layered framework similar to mountainite and rhodesite. It is conceivable that understanding the structure of the ASR product may help developing new technical treatments inhibiting ASR. (C) 2015 Elsevier Ltd. All rights reserved

Iron speciation in blast furnace slag cements

Slag-containing pastes and concretes were analysed by element-specific synchrotron-based techniques to determine the speciation of iron on crushed materials through spatially resolved micro-spectroscopic studies. The investigated cement samples were hydrated either in the laboratory, or exposed to river or sea water. Metallic iron, along with minor proportions of iron sulphide and magnetite was detected in the laboratory sample. Iron sulphide, goethite, and siliceous hydrogarnet were discovered in the blended slag cements hydrated in contact with river water for up to 7 years. In contrast, no Fe(0) was observed in blended concretes exposed to sea water. Instead, iron sulphide, iron(II)-hydroxide and -oxide, hematite, magnetite, siliceous hydrogarnet, and goethite were detected as well as ilmenite (FeTiO3) in the aggregates. The strong acceleration of Fe oxidation in samples exposed to sea water and the long-term passivation observed in the other samples indicate comparable processes as those occurring on steel bars

The Fe-rich clay microsystems in basalt-komatiite lavas: importance of Fe-smectites for pre-biotic molecule catalysis during the Hadean Eon

During the Hadean to early Archean period (4.5–3.5 Ga), the surface of the Earth’s crust was predominantly composed of basalt and komatiite lavas. The conditions imposed by the chemical composition of these rocks favoured the crystallization of Fe-Mg clays rather than that of Al-rich ones (montmorillonite). Fe-Mg clays were formed inside chemical microsystems through sea weathering or hydrothermal alteration, and for the most part, through post-magmatic processes. Indeed, at the end of the cooling stage, Fe-Mg clays precipitated directly from the residual liquid which concentrated in the voids remaining in the crystal framework of the mafic-ultramafic lavas. Nontronite-celadonite and chlorite-saponite covered all the solid surfaces (crystals, glass) and are associated with tiny pyroxene and apatite crystals forming the so-called “mesostasis”. The mesostasis was scattered in the lava body as micro-settings tens of micrometres wide. Thus, every square metre of basalt or komatiite rocks was punctuated by myriads of clay-rich patches, each of them potentially behaving as a single chemical reactor which could concentrate the organics diluted in the ocean water. Considering the high catalytic potentiality of clays, and particularly those of the Fe-rich ones (electron exchangers), it is probable that large parts of the surface of the young Earth participated in the synthesis of prebiotic molecules during the Hadean to early Archean period through innumerable clay-rich micro-settings in the massive parts and the altered surfaces of komatiite and basaltic lavas. This leads us to suggest that Fe,Mg-clays should be preferred to Al-rich ones (montmorillonite) to conduct experiments for the synthesis and the polymerisation of prebiotic molecules