Combination of multi-scale and multi-edge X-ray spectroscopy for investigating the products obtained from the interaction between kaolinite and metallic iron in anoxic conditions at 90 °C

In the context of radioactive waste repository in geological formation, kaolinite-metallic iron interaction in chlorine solution was conducted in batch experiments, under anoxic conditions at 90 °C during 9 months. After a mineralogical characterization at a global scale, products were analyzed at the micrometer and nanometer scales by X-ray absorption spectroscopic techniques (XAS and STXM). Absorption at Al, Si and Fe edges was investigated to have a complete overview of the distribution and status of constituting elements. Whereas Si K-edge results do not evidence significant evolution of silicon status, investigations at Al K-edge and Fe L-edges demonstrate variations at aggregate and particle scales of ^IVAl:^VIAl and Fe²⁺:Fe³⁺ ratios. Spectroscopic data evidence the systematic crystallization of Fe-serpentines onto the remaining particles of kaolinite and the absence of pure species (kaolinite or Fe-serpentines). Combination of spatially resolved spectroscopic analyses and TEM-EDXS elemental distribution aims to calculate unit cell formulae of Fe-serpentines layers and abundance of each species in mixed particles. For most of the investigated particles, results reveal that the variations of particles composition are directly linked to the relative contributions of kaolinite and Fe-berthierine in mixed particles. However, for some particles, microscale investigations evidence crystallization of two other Fe-serpentines species, devoid of aluminum, cronstedtite and greenalite.     

The use of natural and archeological analogues for understanding the long-term behavior of nuclear glasses

The knowledge of the long-term behavior of nuclear waste in anticipation of ultimate disposal in a deep geological formation is of prime importance in a waste management strategy. If phenomenological models have been developed to predict the long-term behavior of these materials, validating these models remains a challenge, when considering the time scale of radioactive decay of radionuclides of environmental concern, typically 10⁴–10⁵ yrs. Here we show how natural or archaeological analogues provide critical constraints not only on the phenomenology of glass alteration and the mechanisms involved, but also on the ability of experimental short-term data to predict long-term alteration in complex environments.     

An XPEEM study of structural cation distribution in swelling clays. I. Synthetic trioctahedral smectites

X-PEEM images and XPS were collected on isolated layers of three synthetic swelling clays, one hectorite and two saponites with various charge, recording the Si(2p), Al(2p) and Mg(2p) core level spectra from the clay sheets. Spectra were fitted to determine the different components of the core levels. Due to their large full width at half maximum, Si XPS spectra were fitted using two to three doublets. It appears that, for a given clay mineral, Si, Al and Mg binding energies (BE) were constant, for all the observed layers. However, variations of the Si BE were observed depending on the nature of the mineral investigated. The various components obtained from the fit of Si spectra could be assigned to different substitution rates; binding energy shifting to lower values with substitution increase in the layer. Furthermore, variations in Si BE according to charge location were assigned to the influence of exchangeable cation.     

The dependence of albite feldspar dissolution kinetics on fluid saturation state at acid and basic pH: Progress towards a universal relation

Here we report on two separate ongoing, multi-year investigations on the dependence of the dissolution rate (R) of albite feldspar on fluid saturation state, as defined by the Gibbs free energy of reaction (ΔG_r) for dissolution. The investigations are based on dissolution at pH 9.2, 150 °C and pH 3.3, 100 °C. Both studies reveal that the R–ΔG_r relation is highly non-linear and sigmoidal. The kinetic data from the first study, being the most complete, can be fitted with a sigmoidal rate curve that is composed of two separate, parallel rate laws that represent distinct mechanisms of dissolution. The switch between one dominant mechanism and the other may be controlled by a critical free energy. The fact that in both studies the same type of sigmoidal R–ΔG_r relation exists for dissolution at different pH and temperature condition suggests that this behavior may be universal for albite and other feldspars. Moreover, the experimental data contradict the commonly used R–ΔG_r relation that is loosely based on transition state theory (TST). This has important implications with respect to the accuracy of geochemical codes that model water–rock interactions at near-equilibrium conditions.     

Late Oligocene post-obduction granitoids of New Caledonia: A case for reactivated subduction and slab break-off

Abstract   In southern New Caledonia, Late Oligocene granodiorite and adamellite are intruded into an ultramafic allochthon emplaced in the Late Eocene period. Previous studies of these granitoids proposed an origin associated with the melting of the underlying continental crust, but our new data show that these high-K to medium-K calc-alkaline granitoids display the geochemical and isotopic features of volcanic arc magmas uncontaminated by crust-derived melts. These magmas were probably generated in a post-Eocene and pre-Miocene subduction, the geophysical traces of which have been detected along the western coast of New Caledonia. Sr, Nd and Pb isotopic ratios indicate derivation from an almost isotopically homogeneous mantle wedge, but in contrast, some variation in trace element ratios uncorrelated to differentiation is indicative of source heterogeneity. Prominent heavy rare earth element (HREE) depletion of some of the younger granitoids may be the result of an equilibrium achieved with garnet-bearing subcrustal material (granulite) found as xenoliths, while a relative Nb, Ta and Hf enrichment, irrespective of crystal fractionation, may be related to either a modest contamination by previously underplated mafic material, heterogeneous hydration of the mantle wedge, or mixing with uplifted Nb-rich mantle. Post-obduction slab break-off can be proposed to have played a role in sublithospheric mantle mixing and the subsequent heterogeneity. The Late Oligocene subduction described here may be tentatively extended southward into northern New Zealand allochthons.     

Iron mineralisation in Mio-Pliocene sediments of the Tamra iron mine (Nefza mining district, Tunisia): Mixed influence of pedogenesis and hydrothermal alteration

The Tamra iron mine (Nefza mining district, N. Tunisia) has been exploited for about one century. There are, however, very few publications modelling the mineralisation within this 50 m-thick Messinian–Zanclean sedimentary series. We present the result of a detailed sedimentological, mineralogical and geochemical study on the siliciclastic sediments heavily mineralised in iron. In their present state of preservation, these are rather unusual sediments, wherein most of sedimentological information is obliterated by iron impregnation. The whole series consists of a succession of fining-upward sequences (a few meters in thickness) that are capped by clay-bearing variegated and mottled horizons, each sequence being interpreted as a shallowing-upward sequence topped by an emersive horizon corresponding to a paleosoil. We propose that alteration and/or pedogenesis by the downward percolation of meteoric fluids accounts for most of the initial iron concentration, while a hydrothermal overprint, linked to the neighbouring Miocene magmatic rocks and associated mineral deposits (Sidi Driss Fe–Pb–Zn mine), accounts for the existing extreme iron enrichment. The proposed model is likely to apply to several other iron mines linked to the Miocene magmatic activity in the whole Maghreb area, and especially along the Apenninic thrust front (locally known as Tell-Rif front).     

An overview of Calanus helgolandicus ecology in European waters

We review current knowledge and understanding of the biology and ecology of the calanoid copepod Calanus helgolandicus in European waters, as well as provide a collaborative synthesis of data from 18 laboratories and 26 sampling stations in areas distributed from the northern North Sea to the Aegean and Levantine Seas. This network of zooplankton time-series stations has enabled us to collect and synthesise seasonal and multi-annual data on abundance, body size, fecundity, hatching success and vertical distribution of C. helgolandicus. An aim was to enable comparison with its congener Calanus finmarchicus, which has been studied intensively as a key component of European and north east Atlantic marine ecosystems. C. finmarchicus is known to over-winter at depth, whereas the life-cycle of C. helgolandicus is less well understood. Overwintering populations of C. helgolandicus have been observed off the Atlantic coast between 400 and 800 m, while in the Mediterranean there is evidence of significant deep-water populations at depths as great as 4200 m. The biogeographical distribution of C. helgolandicus in European coastal waters covers a wide range of habitats, from open ocean to coastal environments, and its contribution to mesozooplankton biomass ranges from 6% to 93%. Highest abundances were recorded in the Adriatic and off the west coast of Spain. C. helgolandicus is generally found in 9-20 °C water, with maximum abundances from 13-17 °C. In contrast, C. finmarchicus is found in cooler water between 0 and 15 °C, with peak abundances from 0 to 9 °C. As water has warmed in the North Atlantic over recent decades, the range of C. helgolandicus and its abundance on the fringes of its expanding range have increased. This review will facilitate development of population models of C. helgolandicus. This will not only help answer remaining questions but will improve our ability to forecast future changes, in response to a warming climate, in the abundance and distribution of this important species.