The influence of aqueous silica on gallium(III) hydrolysis in dilute (2 × 10−4 ≤ mGa ≤ 5 × 10−3) and moderately concentrated (0.02 ≤ mGa ≤ 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 ≤ mSi ≤ 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-Si2-3 species (formed by the substitution of Si in its tri-, tetra- or hexa-cyclic polymers by Ga atoms), and chainlike GaSi2-4 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. 相似文献
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. 相似文献
. Three transgressive–regressive 2nd-order cycles were identified in the Upper Aptian–Albian fluvial and marine deposits of the Lusitanian Basin. Its widespread nature, probably including eustatic origin, allows correlation between the southern package, with precise stratigraphic positioning, and the northern series with a poorly constrained age. The main unconformities can be related to the onset of an oceanic crust, in the western margin of Galicia during the Late Aptian, in the bay of Biscay during the Early Albian, and, to the northwest of the Galicia triple point, during the Middle to Late Albian transition, and, at the Albian–Cenomanian boundary, to a probable compressive event with Africa due to the rotation of Iberia. To cite this article: J. Dinis et al., C. R. Geoscience 334 (2002) 757–764.相似文献
We analyse longitudinal river profiles in southwestern Taiwan. As all necessary data are not available, a physical modelling of river erosion would be subject to large uncertainties. We thus shortcut this modelling and adopt simple empirical exponential equations giving riverbed elevation as a function of downstream distance. We identify a positive altimetric anomaly, which reveals active uplift of an anticline at the front of the fold-and-thrust belt. To cite this article: J. Angelier, R.-F. Chen, C. R. Geoscience 334 (2002) 1103–1111.相似文献
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. 相似文献
Minor granulites (believed to be pre-Triassic), surrounded by abundant amphibolite-facies orthogneiss, occur in the same region as the well-documented Triassic high- and ultrahigh-pressure (HP and UHP) eclogites in the Dabie–Sulu terranes, eastern China. Moreover, some eclogites and garnet clinopyroxenites have been metamorphosed at granulite- to amphibolite-facies conditions during exhumation. Granulitized HP eclogites/garnet clinopyroxenites at Huangweihe and Baizhangyan record estimated eclogite-facies metamorphic conditions of 775–805 °C and ≥15 kbar, followed by granulite- to amphibolite-facies overprint of ca. 750–800 °C and 6–11 kbar. The presence of (Na, Ca, Ba, Sr)-feldspars in garnet and omphacite corresponds to amphibolite-facies conditions. Metamorphic mineral assemblages and P–T estimates for felsic granulite at Huangtuling and mafic granulite at Huilanshan indicate peak conditions of 850 °C and 12 kbar for the granulite-facies metamorphism and 700 °C and 6 kbar for amphibolite-facies retrograde metamorphism. Cordierite–orthopyroxene and ferropargasite–plagioclase coronas and symplectites around garnet record a strong, rapid decompression, possibly contemporaneous with the uplift of neighbouring HP/UHP eclogites.
Carbonic fluid (CO2-rich) inclusions are predominant in both HP granulites and granulitized HP/UHP eclogites/garnet clinopyroxenites. They have low densities, having been reset during decompression. Minor amounts of CH4 and/or N2 as well as carbonate are present. In the granulitized HP/UHP eclogites/garnet clinopyroxenites, early fluids are high-salinity brines with minor N2, whereas low-salinity fluids formed during retrogression. Syn-granulite-facies carbonic fluid inclusions occur either in quartz rods in clinopyroxene (granulitized HP garnet clinopyxeronite) or in quartz blebs in garnet and quartz matrices (UHP eclogite). For HP granulites, a limited number of primary CO2 and mixed H2O–CO2(liquid) inclusions have also been observed in undeformed quartz inclusions within garnet, orthopyroxene, and plagioclase which contain abundant, low-density CO2±carbonate inclusions. It is suggested that the primary fluid in the HP granulites was high-density CO2, mixed with a significant quantity of water. The water was consumed by retrograde metamorphic mineral reactions and may also have been responsible for metasomatic reactions (“giant myrmekites”) occurring at quartz–feldspar boundaries. Compared with the UHP eclogites in this region, the granulites were exhumed in the presence of massive, externally derived carbonic fluids and subsequently limited low-salinity aqueous fluids, probably derived from the surrounding gneisses. 相似文献
The influence of aqueous silica on the hydrolysis of iron(III) nitrate and chloride salts in dilute aqueous solutions (mFe ∼ 0.01 mol/kg) was studied at ambient temperature using X-ray absorption fine structure (XAFS) spectroscopy at the Fe K-edge. Results show that in Si-free iron nitrate and chloride solutions at acid pH (pH < 2.5), Fe is hexa-coordinated with 6 oxygens of H2O- and/or OH-groups in the first coordination sphere of the metal, at an Fe-O distance of 2.00 ± 0.01 Å. With increasing pH (2.7 < pH < 13), these groups are rapidly replaced by bridging hydroxyls (-OH-) or oxygens (-O-), and polymerized Fe hydroxide complexes form via Fe-(O/OH)-Fe bonds. In these polymers, the first atomic shell of iron represents a distorted octahedron with six O/OH groups and Fe-O distances ranging from 1.92 to 2.07 Å. The Fe octahedra are linked together by their edges (Fe-Fe distance 2.92-3.12 Å) and corners (Fe-Fe distance ∼3.47 ± 0.03 Å). The Fe-Fe coordination numbers (Nedge = 1-2; Ncorner = 0.5-0.7) are consistent with the dominant presence of iron dimers, trimers and tetramers at pH 2.5 to 2.9, and of higher-polymerized species at pH > 3.At pH > 2.5 in the presence of aqueous silica, important changes in Fe(III) hydrolysis are detected. In 0.05-m Si solutions (pH ∼ 2.7-3.0), the corner linkages between Fe octahedra in the polymeric complexes disappear, and the Fe-Fe distances corresponding to the edge linkages slightly increase (Fe-Feedge ∼ 3.12-3.14 Å). The presence of 1 to 2 silicons at 3.18 ± 0.03 Å is detected in the second atomic shell around iron. At basic pH (∼12.7), similar structural changes are observed for the iron second shell. The Fe-Si and Fe-Fe distances and coordination numbers derived in this study are consistent with (1) Fe-Si complex stoichiometries Fe2Si1-2 and Fe3Si2-3 at pH < 3; (2) structures composed of Fe-Fe dimers and trimers sharing one or two edges of FeO6-octahedra; and (3) silicon tetrahedra linked to two neighboring Fe octahedra via corners. At higher Si concentration (0.16 m, polymerized silica solution) and pH ∼ 3, the signal of the Fe second shell vanishes indicating the destruction of the Fe-Fe bonds and the formation of different Fe-Si linkages. Moreover, ∼20 mol.% of Fe is found to be tetrahedrally coordinated with oxygens in the first coordination shell (RFe-O = 1.84 Å). This new finding implies that Fe may partially substitute for Si in the tetrahedral network of the silica polymers in Si-rich solutions.The results of this study demonstrate that aqueous silica can significantly inhibit iron polymerization and solid-phase formation, and thus increase the stability and mobility of Fe(III) in natural waters. The silica “poisoning” of the free corner sites of iron-hydroxide colloids should reduce the adsorption and incorporation of trace elements by these colloids in Si-rich natural waters. 相似文献
Kinetic parameters were determined for the first time, via open-system pyrolyses, on algaenans (highly resistant biomacromolecules that are selectively preserved during kerogen formation) isolated from extant microalgae. Parallel studies were also carried out on 10 kerogens exhibiting, with one exception, a low level of maturity. These kerogens included samples chiefly derived from the selective preservation of the above algaenans and samples mainly, or almost exclusively, derived from the “natural vulcanization” pathway. Important differences in activation energy (Ea) distributions were observed between the four algaenans investigated and correlated with their chemical structures. The kerogens predominantly derived from algaenan-selective preservation (Pula alginite, NE 70 and BJ 248 Torbanites, Rundle Oil Shale) also exhibited pronounced differences in Ea distributions. These distributions provided: (i) information on the diversity of the source materials; and (ii) reflected the occurrence of important differences in chemical structures and thermal behaviour between three of the tested kerogens, even though they are all classified as low maturity type I. The Kimmeridge Clay samples and the Lorca Oil Shale showed broad Ea distributions shifted to low energies when compared with the above algaenans and kerogens. Such shifts reflect an important (or even almost exclusive for some of these kerogens) contribution of materials originating from sulphur incorporation into various lipids during early diagenesis. Finally, the kinetic data derived for the nine low maturity fossil samples were extrapolated to a very low, geological heating rate of 3°C Ma−1 and the generation rate curves and cumulative yield curves thus obtained were compared. 相似文献