Geochemical modelling of the weathering zone of the “Mina Fe” U deposit (Spain): A natural analogue for nuclear spent fuel alteration and stability processes in radwaste disposal

The “Mina Fe” U deposit (Salamanca, Spain) has been studied in the context of Enresa’s programme for U-mine sites restoration and also as a natural analogue for processes in high-level nuclear waste (HLNW) geological disposal. The investigations encompassed an array of geoscience disciplines, such as structural geology, mineralogy, hydrogeology and elemental and isotopic geochemistry and hydrogeochemistry of the site. Based on the obtained results, a conceptual mineralogical and geochemical model was performed integrating the main geochemical processes occurring at the site: the interaction between oxidised and slightly acidic water with pyrite, pitchblende, calcite and dolomite, as essential minerals of the U fracture-filling mineralisation, and hydroxyapatite from the host rock, as the main source of P. This conceptual model has been tested in a systematic numerical model, which includes the main kinetic (pyrite and pitchblende dissolution) and equilibrium processes (carbonate mineral dissolution, and goethite, schoepite and autunite secondary precipitation). The results obtained from the reactive-transport model satisfactorily agree with the conceptual model previously established. The assumption of the precipitation of coffinite as a secondary mineral in the system cannot be correctly evaluated due to the lack of hydrochemical data from the reducing zone of the site and valid thermodynamic and kinetic data for this hydrated U(IV)-silicate. This precipitation can also be hampered by the probable existence of dissolved U(IV)-organic matter and/or uranyl carbonate complexes, which are thermodynamically stable under the alkaline and reducing conditions that prevail in the reducing zone of the system. Finally, the intense downwards oxic and acidic alteration in the upper part of the system is of no relevance for the performance assessment of a HLNW disposal. However, the acidic and oxidised conditions are quickly buffered to neutral–alkaline and reducing at very shallow depths, of relevance for the performance assessment of a HLNW repository, even in a natural or artificially perturbed geological environment as “Mina Fe”.     

Weathering of sandstone lotus petals at the Angkor site: a 1,000-year stone durability trial

This article is based on field investigations carried out at Ta Keo and Banteay Srei temples (Angkor, Cambodia), which have similar environmental histories and display the same recurrent decorative pattern (lotus petal) in three different sandstone lithotypes. Based on two original scales of mechanical and chemical weathering, the degree of deterioration of c.2000 sandstone petals was visually assessed, resulting in the proposal of a durability scale. An explanatory scheme was provided, based on laboratory analyses of stone materials (ICP-AES, XRD, SEM-EDS, polarizing microscopy and mercury injection). The key drivers of sandstone durability are both mineralogical and petrophysical. The remarkable preservation of the pink sandstone is due to the quartzose nature of its clasts, the non-swelling clay content of its abundant matrix (kaolinite) and its porosity structure (large connected pores and probable non-connected porosity). The overall good preservation of the green sandstone is due to its extremely low porosity and specific surface area, associated with its strong cementation. The severe deterioration of the grey sandstone is due to its laminated structure (oriented biotites), the susceptibility to hygric swelling and solution of its binding agents (chlorite/smectite and calcite) and its porosity structure, which evolves during a two-stage weathering sequence. The first stage is characterized by a bimodal porosity due to the partial clogging of macropores by swelling clays, and the second stage by a substantial increase in porosity and the penetration of salts (barite and anhydrite). Conversely, oxidation phenomena associated with weathering can lead to a drastic reduction of porosity.     

Precise lead isotope measurements by the double spike technique: A reconsideration

A reappraisal of the “Double Spike Method” for correction of the mass discrimination in lead isotope analysis is presented in view of the possible efficiency of this method, especially as related to the improved performance of the new multi-collector mass spectrometers.First, the effects of mass discrimination during lead isotope analysis, using the silica-gel phosphoric acid method, are discussed in order to verify the validity of the linear discrimination law. In this discussion, we give evidence of a slight bias of the isotopic composition of the SRM 981 NBS lead standard, commonly used for mass discrimination calibrations.A rigorous way to deal with the propagation of the within-run statistical errors on the precision of the double spike correction is then presented. This allows the optimization of the parameters of the method (spike isotopic composition and precision, spiking proportion) and the calculation of the respective error associated with each corrected isotopic ratio. The perturbation of the double spike correction due to analytical contamination, which has caused previous failure in the application of the method, is avoided by preparation of the mixture between the spike and the sample at the very end of the chemical separation procedure.Using a single collector mass spectrometer, examples of application on lead standards and on a set of samples suggest a possible improvement in the precision by a factor of 3 compared to the usual method of fractionation normalization and confirm the usefulness of the method with the new generation of mass spectrometers.     

Differences in the quality of polishing between sound and weathered granites

Aesthetic characteristics are important when rocks are used as construction materials. Among all the surface finishes available, the polished finish is the one which best enhances the rock attractiveness. Colour (C), roughness (R) and gloss (G) are surface properties usually used to assess the rock polishing. In this research, the CRG properties were assessed in polished samples of three ornamental granites with different textures and physical–mechanical properties, one weathered and two sound. C was evaluated in CIE-L ^* a ^* b ^* and CIE-L ^* C ^* _ab h _ab systems, R with R _a and R _z parameters and G using the 20°, 60° and 85° geometries. The weathered granite presents a noticeable colour variation, especially in the b ^* parameter, while the sound ones have a more homogeneous colour. Sound and more textural homogeneous granites have a low surface roughness and high gloss, which are uniformly distributed. The weathered granite shows a higher surface roughness and lower gloss, with scattered distribution. The mineral contacts are the main cause of the surface irregularities. The results show the interdependence between the CRG properties and stress the importance of the polishing process for enhancing the aesthetic characteristics of the granites. CRG properties could be used for quality control in granite processing plants, thus avoiding noticeable differences in the facades of buildings, particularly when weathered granites are used.     

Experimental transport of Si,Al and Mg in hydrothermal solutions: an application to vein mineralization during high-pressure,low-temperature metamorphism in the French Alps

A study of hydrothermal vein mineralization in meta-argillites subjected to high-pressure, low-temperature metamorphism reveals that ferromagnesian (e.g., chlorite) and pure aluminosilicate (e.g., pyrophyllite) mineralization can be correlated with regimes of increasing and decreasing temperature, respectively. An experimental study of the transport of silica, aluminum and magnesium in hydrothermal solutions has been undertaken to simulate variations in the physical conditions during metamorphism and the accompanying mass transport in a closed system. Thermodynamic and kinetic analysis of the experimental results indicates that local equilibrium among aqueous and mineral phases controls the distribution and composition of hydrothermal vein mineralization and that vein mineralogy can be used to infer the sense of variation of pressure and temperature during metamorphism.     

In vitro simulation of oxic/suboxic diagenesis in an estuarine fluid mud subjected to redox oscillations

Estuarine turbidity maxima (ETMs) are sites of intense mineralisation of land-derived particulate organic matter (OM), which occurs under oxic/suboxic oscillating conditions owing to repetitive sedimentation and resuspension cycles at tidal and neap-spring time scales. To investigate the biogeochemical processes involved in OM mineralisation in ETMs, an experimental set up was developed to simulate in vitro oxic/anoxic oscillations in turbid waters and to follow the short timescale changes in oxygen, carbon, nitrogen, and manganese concentration and speciation. We present here the results of a 27-day experiment (three oxic periods and two anoxic periods) with an estuarine fluid mud from the Gironde estuary. Time courses of chemical species throughout the experiment evidenced the occurrence of four distinct characteristic periods with very different properties. Steady oxic conditions were characterised by oxygen consumption rates between 10 and 40 μmol L⁻¹ h⁻¹, dissolved inorganic carbon (DIC) production of 9–12 μmol L⁻¹ h⁻¹, very low NH₄⁺ and Mn²⁺ concentrations, and constant NO₃⁻ production rates (0.4 - 0.7 μmol L⁻¹ h⁻¹) due to coupled ammonification and nitrification. The beginning of anoxic periods (24 h following oxic to anoxic switches) showed DIC production rates of 2.5–8.6 μmol L⁻¹ h⁻¹ and very fast NO₃⁻ consumption (5.6–6.3 μmol L⁻¹ h⁻¹) and NH₄⁺ production (1.4–1.5 μmol L⁻¹ h⁻¹). The latter rates were positively correlated to NO₃⁻ concentration and were apparently caused by the predominance of denitrification and dissimilatory nitrate reduction to ammonia. Steady anoxic periods were characterised by constant and low NO₃⁻ concentrations and DIC and NH₄⁺ productions of less than 1.3 and 0.1 μmol L⁻¹ h⁻¹, respectively. Mn²⁺ and CH₄ were produced at constant rates (respectively 0.3 and 0.015 μmol L⁻¹ h⁻¹) throughout the whole anoxic periods and in the presence of nitrate. Finally, reoxidation periods (24–36 h following anoxic to oxic switches) showed rapid NH₄⁺ and Mn²⁺ decreases to zero (1.6 and 0.8–2 μmol L⁻¹ h⁻¹, respectively) and very fast NO₃⁻ production (3 μmol L⁻¹ h⁻¹). This NO₃⁻ production, together with marked transient peaks of dissolved organic carbon a few hours after anoxic to oxic switches, suggested that particulate OM mineralisation was enhanced during these transient reoxidation periods. An analysis based on C and N mass balance suggested that redox oscillation on short time scales (day to week) enhanced OM mineralisation relative to both steady oxic and steady anoxic conditions, making ETMs efficient biogeochemical reactors for the mineralisation of refractory terrestrial OM at the land-sea interface.     

Prometheus and Pandora: masses and orbital positions during the Cassini tour

Hubble Space Telescope (HST) images of Prometheus and Pandora show longitude discrepancies of about 20° with respect to the Voyager ephemerides, with an abrupt change in mean motion at the end of 2000 (French et al., 2003, Icarus 162, 143-170; French and McGhee, 2003, Bull. Am. Astron. Soc. 34, 06.07). These discrepancies are anti-correlated and arise from chaotic interactions between the two moons, occurring at interval of 6.2 yr, when their apses are anti-aligned (Goldreich and Rappaport, 2003a, Icarus 162, 391-399). This behavior is attributed to the overlap of four 121:118 apse-type mean motion resonances (Goldreich and Rappaport, 2003b, Icarus 166, 320-327). We study the Prometheus-Pandora system using a Radau-type integrator taking into account Saturn's oblateness up to and including terms in J₆, plus the effects of the major satellites. We first confirm the chaotic behavior of Prometheus and Pandora. By fitting the numerical integrations to the HST data (French et al., 2003, Icarus 162, 143-170; French and McGhee, 2003, Bull. Am. Astron. Soc. 34, 06.07), we derive the satellite masses. The resulting GM values (with their standard 3-σ errors) for Prometheus and Pandora are respectively and . Using the nominal shape of the two moons (Thomas, 1989, Icarus 77, 248-274), we derive Prometheus and Pandora's densities, 0.40^+0.03_−0.07 and 0.49^+0.05_−0.09 g cm⁻³, respectively. Our numerical fits also enable us to constrain the time of the latest apse anti-alignment in 2000. Finally, using our fit, we predict the orbital positions of the two satellites during the Cassini tour, and provide a lower limit of the uncertainties due to chaos. These uncertainties amount to about 0.2° in mean longitude at the arrival of the Cassini spacecraft in July 2004, and to about 3° in 2008, at the end of the nominal tour.     

Structure and evolution of the Bay of Pozzuoli (Italy) using marine seismic reflection data: implications for collapse of the Campi Flegrei caldera

Digital marine seismic reflection data acquired in 1973 in the Bay of Pozzuoli, and recently reprocessed, were used to study the volcanological evolution of the marine sector of Campi Flegrei Caldera during the last 37 ka. In order to gain more information, interpretation also involved estimation of the "pseudo-velocity" and the "pseudo-density" from the resistivity logs of two onshore deep exploration wells. The main results are: (1) discovery of ancient pre-18 ka and post-37 ka submarine and mainly effusive volcanic activity, along coeval emission centers located at the edges of Campi Flegrei Caldera; (2) confirmation that the caldera collapse in the marine sector of Campi Flegrei seems strongly controlled by regional NE–SW and NW–SE structural discontinuities; (3) the finding of at least two episodes of collapse in the bay; and (4) identification of a post-18 ka volcanic deflation phase that has caused about 150–200 m of subsidence in the central sector of the Bay of Pozzuoli in the last 18 ka.Editorial responsibilty: T. Druitt     

Monitoring chemical contamination levels in the Mediterranean based on the use of mussel caging

Within the framework of the biointegrator network (RINBIO), 92 man-made cages containing mussels (Mytilus galloprovincialis), distributed over 1800 km of the French Mediterranean coast, made it possible to assess chemical contamination by heavy metals (Cd, Hg, Zn, Pb, Cu, Ni, Cr, As) and organic compounds (DDT, PCBs, HAP). The caging technique was adopted to compensate for the scarcity of natural shellfish stocks in the Mediterranean and to enable comparison of the sites regardless of their physicochemical and trophic characteristics. Models linking a biometric parameter (the condition index) to pollutant levels make it possible to adjust raw data on contamination for a reference individual, by making a clear distinction between physiological factors (growth) and environmental ones. The results demonstrate significant levels of pollutants in sites heretofore unsampled; the pollution occurs at limited areas, and the sources have been identified. Moreover, average contamination levels are comparable to those measured in wild species and in other areas. Overall, the research demonstrates the reliability of this methodological approach for monitoring marine pollution, especially in the Mediterranean.