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Gleb S Pokrovski Jacques SchottJean-Louis Hazemann François Farges Oleg S Pokrovsky 《Geochimica et cosmochimica acta》2002,66(24):4203-4222
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
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Gleb S Pokrovski Jacques Schott Jean-Louis Hazemann 《Geochimica et cosmochimica acta》2003,67(19):3559-3573
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
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Optimization of mooring observations in Northern Bering Sea 总被引：1，自引：0，他引：1
The problem of the optimal sampling strategy for moored current velocity observations in the Northern Bering Sea is addressed. We analyze dynamically induced correlations in the North Bering Sea currents and conduct their sensitivity analysis to optimize positions of a limited number of moorings. Optimization of the sampling strategy is performed with respect to robustness of the reconstruction of the North Bering Sea circulation with a particular emphasis on the accurate monitoring of the mean Bering Strait transport. Computations reveal four major regions in the North Bering Sea basin that are highly correlated with the Bering Strait transport. Apart from the regions within the Bering Strait itself, they include the Anadyr Strait and a region 100 km south of the Cape of Prince of Wales. Results of the sensitivity analysis are tested in the framework of twin data experiments with the quasi-stationary and oscillatory background circulations. 相似文献
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In recent years, monitoring offshore surface circulation in the Arctic Ocean with high frequency radars has become an issue of increasing practical importance. In this study, radar positions are optimized by minimizing the reconstruction errors of the surface currents in the Southeastern Chukchi Sea. By means of an adjoint sensitivity technique it is shown that in the case of a pair of radars, their optimal (i.e. most favorable) location is at Kivalina, a settlement near the strongest outflow of the Alaskan Coastal Current from the monitored domain. The least favorable location is at Shishmaref, a settlement near relatively weak inflow into the region as observed from the coast. However, if two pairs of radars are available, the best locations are Kivalina and Shishmaref. The results are verified using observational system simulation experiments (OSSEs) performed in the framework of a 4-dimensional variational assimilation of simulated radar observations into a numerical model. It is shown that correct specification of the first guess solution is of primary importance for obtaining realistic results from both adjoint sensitivity analysis and OSSEs. This emphasizes the necessity of obtaining accurate high resolution climatologies for future ice-free offshore regions in the Arctic. 相似文献
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Hekinian R. Juteau T. Gràcia E. Sichler B. Sichel S. Udintsev G. Apprioual R. Ligi M. 《Marine Geophysical Researches》2000,21(6):529-560
The St. Paul F.Z. is a large structural domain made up of multiple transform faults interrupted by several Intra-Transform Ridge (ITR) spreading segments. Two regions were studied in details by submersible: (1) The ITR short (<20 km in length) segment near 0° 37N–25° 27W and 1° N–27° 42W and (2) The St. Peter and St. Paul's Rocks (SPPR) massif located at 29° 25W (¡3700 m depth). (1) The short ITR segments consist of a magma starved rift valley with recent volcanic activities at 4700 m depth. A geological profile made along the rift valley wall showed localized volcanics (basalts and dykes) which are believed to overlay and intrude the ultramafics. The geological setting and the high ultramafic/volcanic ratio suggest an extremely low magmatic supply and crustal-mantle uplift during lithospheric stretching and denudation. (2) The St. Peter and St. Paul's Rocks (SPPR) massif consists of a sigmoidal ridge within the active transform zone. The SPPR is divided into two different geological domains called the North and the South Ridges. The North Ridge consists of strongly tectonized fault scarps composed of banded and mylonitized peridotite, sporadic gabbros (3900–2500 m) and metabasalts (2700–1700 m). The South Ridge is less tectonized with undeformed, serpentinized spinel lherzolite (2000–1400 m) and basalts. Extensional motion and denudation accompanied by diapirism affected the South Ridge within a transform domain. Instead, the North Ridge was formed during an important strike-slip and faulting motion resulting in the uplifted portion of the St. Paul F.Z. transverse ridge. There is a regional compositional variation of the volcanics where E-MORBs and alkali basalts are produced on the SPPR massif and are comparable to the adjacent northern segments of the Mid-Atlantic Ridge. On the other hand, N and T- MORBs collected from the eastern part of the St. Paul F.Z. (25° 27W IRT) are similar to the volcanics from the southern segments of the MAR. The peridotites exposed in these provinces (SPPR and ITR) are similar in their REE and trace element distribution. Different degrees (3–15%) of partial melting of a mixed composite mantle consisting of spinel and amphibole bearing lherzolite veined with 5–40% clinopyroxenite gave rise to the observed MORBs and alkali basalts. 相似文献
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Antimony speciation in saline hydrothermal fluids: A combined X-ray absorption fine structure spectroscopy and solubility study 总被引：2，自引：0，他引：2
Gleb S. Pokrovski Anastassia Yu. Borisova Jean-Louis Hazemann Marie Tella 《Geochimica et cosmochimica acta》2006,70(16):4196-4214
Solubility of senarmontite (Sb2O3, cubic) in pure water and NaCl-HCl aqueous solutions, and local atomic structure around antimony in these fluids were characterized using in situ X-ray absorption fine structure (XAFS) spectroscopy at temperatures to 450 °C and pressures to 600 bars. These experiments were performed using a new X-ray cell which allows simultaneous measurement of the absolute concentration of the absorbing element in the fluid, and atomic environment around the absorber. Results show that aqueous Sb(III) speciation is dominated by the complex in pure water, mixed Sb-hydroxide-chloride complexes in acidic NaCl-HCl solutions (2 m NaCl-0.1 m HCl), and by Sb-chloride species in concentrated HCl solutions (3.5 m HCl). Interatomic Sb-O and Sb-Cl distances in these complexes range from 1.96 to 1.97 Å and from 2.37 to 2.47 Å, respectively. These structural data, together with senarmontite solubility determined from XAFS spectra, were complemented by batch-reactor measurements of senarmontite and stibnite (Sb2S3, rhombic) solubilities over a wide range of HCl and NaCl concentrations from 300 to 400 °C. Analysis of the whole dataset shows that Sb(III) speciation in high-temperature moderately acid (pH > 2-3) Cl-rich fluids is dominated by mixed hydroxy-chloride species like Sb(OH)2Cl° and Sb(OH)3Cl−, but other species containing two or three Cl atoms appear at higher acidities and moderate temperatures (?300 °C). Calculations using stability constants retrieved in this study indicate that mixed hydroxy-chloride complexes control antimony transport in saline high-temperature ore fluids at acidic conditions. Such species allow for a more effective Sb partitioning into the vapor phase during boiling and vapor-brine separation processes occurring in magmatic-hydrothermal systems. Antimony hydroxy-chloride complexes are however minor in the neutral low- to moderate-temperature solutions (?250-300 °C) typical of Sb deposits formation; the antimony speciation in these systems is dominated by Sb(OH)3 and potentially Sb-sulfide species. 相似文献
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The main results of seismic investigations in the transition zone from the Asian continent to the Pacific Ocean and in several regions of the Pacific Ocean are reported briefly. One of the most surprising findings is the existence of a layer with a P-velocity of 9 km/sec only 12–15 km below the oceanic crust-mantle boundary. Some recommendations for future investigations are given. 相似文献