An X-ray absorption fine structure and nuclear magnetic resonance spectroscopy study of gallium-silica complexes in aqueous solution

The influence of aqueous silica on gallium(III) hydrolysis in dilute (2 × 10⁻⁴ ≤ m_Ga ≤ 5 × 10⁻³) and moderately concentrated (0.02 ≤ m_Ga ≤ 0.3) aqueous solutions was studied at ambient temperature, using high resolution X-ray absorption fine structure (XAFS) and nuclear magnetic resonance (NMR) spectroscopies, respectively. Results show that, in Si-free acidic solutions (pH < 3), Ga is hexa-coordinated with oxygens of H₂O molecules and/or OH groups in the first coordination sphere of the metal. With increasing pH, these hydroxyl groups are progressively replaced by bridging oxygens (-O-), and polymerized Ga-hydroxide complexes form via Ga-O-Ga chemical bonds. In the 2.5-3.5 pH range, both XAFS and NMR spectra are consistent with the dominant presence of the Ga₁₃ Keggin polycation, which has the same local structure as A1₁₃. Under basic pH (pH > 8), Ga exhibits a tetrahedral coordination, corresponding to Ga(OH)₄⁻ species, in agreement with previous NMR and potentiometric studies. Major changes in Ga hydrolysis have been detected in the presence of aqueous silica. Ga is tetra-coordinated, both in basic and acid (i.e., at pH > 2.7) Si-bearing solutions (0.01 ≤ m_Si ≤ 0.2), and forms stable gallium-silicate complexes. In these species, Ga binds via bridging oxygen to 2 ± 1 silicons, with an average Ga-Si distance of 3.16 ± 0.05 Å, and to 2 ± 1 silicons, with an average Ga-Si distance of 3.39 ± 0.03 Å. These two sets of Ga-Si distances imply the formation of two types of Ga-silicate aqueous complex, cyclic Ga-Si_2-3 species (formed by the substitution of Si in its tri-, tetra- or hexa-cyclic polymers by Ga atoms), and chainlike GaSi_2-4 species (similar to those found for A1), respectively. The increase in the number of Si neighbors (a measure of the complex concentration and stability), in alkaline media, with increasing SiO₂(aq) content and decreasing pH is similar to that for A1-Si complexes found in neutral to basic solutions. At very acid pH and moderate silica concentrations, the presence of another type of Ga-Si complex, in which Ga remains hexa-coordinated and binds to the silicon tetrahedra via the GaO₆ octahedron corners, has also been detected. These species are similar to those found for Al³⁺ in acid solutions. Thus, as for aluminum, silicic acid greatly hampers Ga hydrolysis and enhances Ga mobility in natural waters via the formation of gallium-silicate complexes.     

Comparison between the Chile and Mexico triple junction areas substantiates slab window development beneath northwestern Mexico during the past 12-10 Myr

When combined with the Miocene-Recent volcanic record of Baja California, a parallel drawn between the Chile and Mexico triple junction areas substantiates slab window development beneath northwestern Mexico during the past 12-10 Myr. The slab-free zone manifestations challenge the notion that ridge subduction has not occurred beneath the southern Baja California peninsula. The geochemically distinctive rocks from the Santa Clara volcanic field of west-central Baja California, including coeval adakites and niobium-enriched basalt, are commonly inferred to signal partial melting of the subducting plate at shallow depths and relatively high temperatures, before slab dehydration occurs. Such PT conditions for slab melting have only been observed in association with spreading-ridge subduction. We propose that slab window development beneath southern Baja California and mainland Mexico (30° to 18°N) resulted from subduction of the East Pacific rise.     

Paléoenvironnements et caractérisation des roches mères pétrolières des séries pré-salifères du bassin intérieur du Gabon

The Interior Basin of Gabon, created during the break-up between South America and Africa, displays thick Neoproterozoic to Aptian p.p. fluvio-lacustrine deposits overlain by Aptian to Albian marine facies. Rock–Eval analyses from outcrop and drillhole samples show high content in organic matter (up to 25%) related to types I and II. These intervals are encountered within Permian, Neocomian–Barremian as well as Aptian siliciclastic succession. They constitute fairly good to excellent potential petroleum source rocks, which are most probably at the origin of oil indices recognized both in drillholes and in surface.     

Simplified vibratory characterization of alluvial basins

For the analysis of seismic wave amplification, modal methods are interesting tools to study the modal properties of geological structures. Modal approaches mainly lead to information on such parameters as fundamental frequencies and eigenmodes of alluvial basins. For a specific alluvial deposit in Nice (France), a simplified modal approach involving the Rayleigh method is considered. This approach assumes a set of admissible shape functions for the eigenmodes and allows a fast estimation of the fundamental frequency of the basin. The agreement with other numerical results (Boundary Element Method) and experimental ones is fully satisfactory. The simplified modal method then appears as an efficient mean for the global vibratory characterization of geological structures towards resonance. To cite this article: J.-F. Semblat et al., C. R. Geoscience 335 (2003).     

Wrench tectonics flip at oblique subduction. A model from New Zealand

In eastern North Island New Zealand, oblique subduction of the Pacific Plate beneath the Australian Plate is associated with strain partitioning. Dextral along-strike component of displacement occurred first at Early Miocene major faults within the eastern fore-arc domain. These faults were active from Early Miocene to Pliocene times. Since Pliocene times, most of the movement occurs at western faults such as the Wellington Fault. The latter joins the back-arc domain to the north. The jump of wrench faulting is related to the oblique opening of the back-arc domain. Both phenomena are impeded southwards by the Hikurangi oceanic plateau entering the subduction zone. To cite this article: J. Delteil et al., C. R. Geoscience 335 (2003).     

Timing of deformation in the Norseman-Wiluna Belt, Yilgarn Craton, Western Australia

Establishing relative and absolute time frameworks for the sedimentary, magmatic, tectonic and gold mineralisation events in the Norseman-Wiluna Belt of the Archean Yilgarn Craton of Western Australia, has long been the main aim of research efforts. Recently published constraints on the timing of sedimentation and absolute granite ages have emphasized the shortcomings of the established rationale used for interpreting the timing of deformation events. In this paper the assumptions underlying this rationale are scrutinized, and it is shown that they are the source of significant misinterpretations. A revised time chart for the deformation events of the belt is established. The first shortening phase to affect the belt, D₁, was preceded by an extensional event D_1e and accompanied by a change from volcanic-dominated to plutonic-dominated magmatism at approximately 2685–2675 Ma. Later extension (D_2e) controlled deposition of the ca 2655 Ma Kurrawang Sequence and was followed by D₂, a major shortening event, which folded this sequence. D₂ must therefore have started after 2655 Ma—at least 20 Ma later than previously thought and after the voluminous 2670–2655 Ma high-Ca granite intrusion. Younger transcurrent deformation, D₃–D₄, waned at around 2630 Ma, suggesting that the crustal shortening deformation cycle D₂–D₄ lasted approximately 20–30 Ma, contemporaneous with low-volume 2650–2630 Ma low-Ca granites and alkaline intrusions. Time constraints on gold deposits suggest a late mineralisation event between 2640–2630 Ma. Thus, D₂–D₄ deformation cycle and late felsic magmatism define a 20–30 Ma long tectonothermal event, which culminated with gold mineralisation. The finding that D₂ folding took place after voluminous high-Ca granite intrusion led to research into the role of competent bodies during folding by means of numerical models. Results suggest that buoyancy-driven doming of pre-tectonic competent bodies trigger growth of antiforms, whereas non-buoyant, competent granite bodies trigger growth of synforms. The conspicuous presence of pre-folding granites in the cores of anticlines may be a result from active buoyancy doming during folding.     

Rivers, chemical weathering and Earth's climate

We detail the results of recent studies describing and quantifying the large-scale chemical weathering of the main types of continental silicate rocks: granites and basalts. These studies aim at establishing chemical weathering laws for these two lithologies, describing the dependence of chemical weathering on environmental parameters, such as climate and mechanical erosion. As shown within this contribution, such mathematical laws are of primary importance for numerical models calculating the evolution of the partial pressure of atmospheric CO₂ and the Earth climate at geological timescales. The major results can be summarized as follow: (1) weathering of continental basaltic lithologies accounts for about 30% of the total consumption of atmospheric CO₂ through weathering of continental silicate rocks. This is related to their high weatherability (about eight times greater than the granite weatherability); (2) a simple weathering law has been established for basaltic lithologies, giving the consumption of atmospheric CO₂ as a function of regional continental runoff, and mean annual regional temperature; (3) no such simple weathering law can be proposed for granitic lithologies, since the effect of temperature can only be identified for regions displaying high continental runoff; (4) a general law relating mechanical erosion and chemical weathering has been validated on small and large catchments. The consequences of these major advances on the climatic evolution of the Earth are discussed. Particularly, the impacts of the onset of the Deccan trapps and the Himalayan orogeny on the global carbon cycle are reinvestigated. To cite this article: B. Dupré et al., C. R. Geoscience 335 (2003).     

Re-Os Isotopic Measurements at the Femtomole Level in Natural Samples

Here we describe a new chemical separation method for Os and an improved mass spectrometric procedure for Re and Os. This technique is based on the selective extraction of OsO₄ from aqueous solution in liquid bromine. Among other advantages, this procedure avoids the cumbersome distillation procedure for Os and uses only commercial "off the shelf" PFA teflon labware. Blank levels for 0.5 g sample sizes are: 0.06 pg and 0.5 pg for Os and Re respectively. Samples containing as little as 1 pg g⁻¹ Os can be analysed reliably with this method. Adaptation to other dissolution methods is also discussed.     

The Distribution of Redox Sensitive Elements (U, As, Sb, V and Mo) along a River-Wetland-Lake System (Balaton Region, Hungary)

The distribution of redox sensitive elements (U, As,Sb, Mo and V) has been investigated in Lake Balatonand two man-made reservoirs (Lake Kis-Balaton-1 andKis-Balaton-2) built along the River Zala, the mainriver discharging into it. These elements underwentremoval in Lake Kis Balaton-2 (KB-2) during anoxicconditions (May and September).Similarities were found between the distributions ofdissolved As and Sb. Both elements had elevateddissolved concentrations in Lake Kis-Balaton-1 (KB-1)and in Lake Balaton in September. This increasedmobility could be due to a change of speciation (viareduction and the formation of methylated species).Such changes in speciation are well documented in theliterature and are generally enhanced during periodsof warmth and high primary productivity.Dissolved V and Mo distributions also showedsimilarities with higher concentrations in LakeBalaton than in other parts of the system.Although removal is not clearly detected from thedissolved concentrations, U, As, Sb and Mo aresignificantly enriched in the organic-rich sedimentsof Lake KB-1, while V is mainly associated with thealumino-silicate fraction. In Lake KB-1, theconcentrations of all elements in SPM (suspendedparticulate matter) are lower than in the depositedsediments (except for As) suggesting that enrichmentprocesses are occuring in the deposited sediments.Additionnally the cycling of As and Mo can be alsopartly controlled by uptake and scavenging processesin the water column, as suggested by the elevated Asand Mo concentrations observed in SPM seasonnally forAs in Lake KB-1 and at Z.mouth-1 station and for Mo atZ.mouth-1 station and Lake Balaton.