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51.
Metagabbros and amphibolites exposed in the Bou-Maïza area of the Edough massif (northeast Algeria) are described in detail. Field and petro-structural observations point to the syn-sedimentary emplacement of gabbros as clasts, blocks and lenses of polymictic gabbroic breccias. Associated amphibolites display fine-scale parallel sedimentary bedding and represent mafic epiclastites, litharenites and mafic greywackes. The mafic beds and lenses are intercalated with aluminous pelitic schists of continental origin, quartzite and marble. It is concluded that all mafic rocks from this locality derive from the erosion of an oceanic plutono-volcanic complex of MORB affinity that was reworked in a block matrix mélange and emplaced as turbidites and debris flows during the Mesozoic. We propose a convergent plate margin setting for these formations connected with the subducted Calabrian branch of the Tethyan slab.  相似文献   
52.
We present experimental and calculated Al K-edge X-ray absorption near-edge structure (XANES) spectra of aluminous goethite with 10–33 mol% of AlOOH and diaspore. Significant changes are observed experimentally in the near- and pre-edge regions with increasing Al concentration in goethite. First-principles calculations based on density functional theory (DFT) reproduce successfully the experimental trends. This permits to identify the electronic and structural parameters controlling the spectral features and to improve our knowledge of the local environment of \(\hbox {Al}^{3+}\) in the goethite–diaspore partial solid solution. In the near-edge region, the larger peak spacing in diaspore compared to Al-bearing goethite is related to the nature (Fe or Al) of the first cation neighbours around the absorbing Al atom (Al*). The intensity ratio of the two near-edge peaks, which decreases with Al concentration, is correlated with the average distance of the first cations around Al* and the distortion of the \(\hbox {AlO}_6\) octahedron. Finally, the decrease in intensity of the pre-edge features with increasing Al concentration is due to the smaller number of Fe atoms in the local environment of Al since Al atoms tend to cluster. In addition, it is found that the pre-edge features of the Al K-edge XANES spectra enable to probe indirectly empty 3d states of Fe. Energetic, structural and spectroscopic results suggest that for Al concentrations around 10 mol%, Al atoms can be considered as isolated, whereas above 25 mol%, Al clusters are more likely to occur.  相似文献   
53.
The smectite-to-chlorite conversion is investigated through long-duration experiments (up to 9 years) conducted at 300 °C. The starting products were the Wyoming bentonite MX80 (79 % smectite), metallic iron and magnetite in contact with a Na–Ca chloride solution. The predominant minerals in the run products were an iron-rich chlorite (chamosite like) and interstratified clays interpreted to be chlorite/smectite and/or corrensite/smectite, accompanied by euhedral crystals of quartz, albite and zeolite. The formation of pure corrensite was not observed in the long-duration experiments. The conversion of smectite into chlorite over time appears to take place in several steps and through several successive mechanisms: a solid-state transformation, significant dissolution of the smectite and direct precipitation from the solution, which is over-saturated with respect to chlorite, allowing the formation of a chamosite-like mineral. The reaction mechanisms are confirmed by X-ray patterns and data obtained on the experimental solutions (pH, contents of Si, Mg, Na and Ca). Because of the availability of some nutrients in the solution, total dissolution of the starting smectite does not lead to 100 % crystallization of chlorite but to a mixture of two dominant clays: chamosite and interstratified chlorite/smectite and/or corrensite/smectite poor in smectite. The role of Fe/(Fe + Mg) in the experimental medium is highlighted by chemical data obtained on newly formed clay particles alongside previously published data. The newly formed iron-rich chlorite has the same composition as that predicted by the geothermometer for diagenetic to low-grade metamorphic conditions, and the quartz + Fe-chlorite + albite experimental assemblage in the 9-year experiment is close to that fixed by water–rock equilibrium.  相似文献   
54.
The New Caledonia ophiolite(Peridotite Nappe)consists primarily of harzburgites,locally overlain by mafic-ultramafic cumulates,and minor spinel and plagioclase lherzolites.In this study,a comprehensive geochemical data set(major and trace element,Sr-Nd-Pb isotopes)has been obtained on a new set of fresh harzburgites in order to track the processes recorded by this mantle section and its evolution.The studied harzburgites are low-strain tectonites showing porphyroclastic textures,locally grading into protomylonitic textures.They exhibit a refractory nature,as attested by the notable absence of primary clinopyroxene,very high Fo content of olivine(91-93 mol.%),high Mg#of orthopyroxene(0.91-0.93)and high Cr#of spinel(0.44-0.71).The harzburgites are characterised by remarkably low REE concentrations(<0.1 chondritic values)and display"U-shaped"profiles,with steeply sloping HREE(DyN/YbN=0.07-0.16)and fractionated LREE-MREE segments(LaN/SmN=2.1-8.3),in the range of modern fore-arc peridotites.Geochemical modelling shows that the HREE composition of the harzburgites can be reproduced by multi-stage melting including a first phase of melt depletion in dry conditions(15%fractional melting),followed by hydrous melting in a subduction zone setting(up to 15%-18%).However,melting models fail to explain the enrichments observed for some FME(i.e.Ba,Sr,Pb),LREE-MREE and Zr-Hf.These enrichments,coupled with the frequent occurrence of thin,undeformed films of Al2 O3,and CaO-poor orthopyroxene(Al2O3=0.88-1.53 wt.%,CaO=0.31-0.56 wt.%)and clinopyroxene with low Na2 O(0.03-0.16 wt.%),Al2 O3(0.66-1.35 wt.%)and TiO2(0.04-0.10 wt.%)contents,point to FME addition during fluid-assisted melting followed by late stage metasomatism most likely operated by subductionrelated melts with a depleted trace element signature.Nd isotopic ratios range from unradiogenic to radiogenic(-0.80<εNdi≤+13.32)and negatively correlate with Sr isotopes(0.70257≤87Sr/86Sr≤0.70770).Pb isotopes cover a wide range,trending from DMM toward enriched,sediment-like,compositions.We interpret the geochemical signature displayed by the New Caledonia harzburgites as reflecting the evolution of a highly depleted fore-arc mantle wedge variably modified by different fluid and melt inputs during Eocene subduction.  相似文献   
55.
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.  相似文献   
56.
57.
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.  相似文献   
58.
59.
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.  相似文献   
60.
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 (ΔGr) 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–ΔGr 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–ΔGr 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–ΔGr 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.  相似文献   
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