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The crystallographic structures of the synthetic cheralite, CaTh(PO4)2, and its homolog CaNp(PO4)2 have been investigated by X-ray diffraction at room temperature. Rietveld analyses showed that both compounds crystallize in the monoclinic system and are isostructural to monazite LnPO4 (Ln = La to Gd). The space group is P21/n (I.T. = 14) with Z = 2. The refined lattice parameters of CaTh(PO4)2 are a = 6.7085(8) Å, b = 6.9160(6) Å, c = 6.4152(6) Å, and β = 103.71(1)° with best fit parameters R wp = 4.87%, R p = 3.69% and R B = 3.99%. For CaNp(PO4)2, we obtained a = 6.6509(5) Å, b = 6.8390(3) Å, c = 6.3537(8) Å, and β = 104.12(6)° and R wp = 6.74%, R p = 5.23%, and R B = 6.05%. The results indicate significant distortions of bond length and angles of the PO4 tetrahedra in CaTh(PO4)2 and to a lesser extent in CaNp(PO4)2. The structural distortions were confirmed by Raman spectroscopy of CaTh(PO4)2. A comparison with the isostructural compounds LnPO4 (Ln = Ce and Sm) confirmed that the substitution of the large rare earth trivalent cations with Ca2+ and Th4+ introduces a distortion of the PO4 tetrahedra.  相似文献   
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The solubility of CO2 in dacitic melts equilibrated with H2O-CO2 fluids was experimentally investigated at 1250°C and 100 to 500 MPa. CO2 is dissolved in dacitic glasses as molecular CO2 and carbonate. The quantification of total CO2 in the glasses by mid-infrared (MIR) spectroscopy is difficult because the weak carbonate bands at 1430 and 1530 cm−1 can not be reliably separated from background features in the spectra. Furthermore, the ratio of CO2,mol/carbonate in the quenched glasses strongly decreases with increasing water content. Due to the difficulties in quantifying CO2 species concentrations from the MIR spectra we have measured total CO2 contents of dacitic glasses by secondary ion mass spectrometry (SIMS).At all pressures, the dependence of CO2 solubility in dacitic melts on xfluidCO2,total shows a strong positive deviation from linearity with almost constant CO2 solubility at xCO2fluid > 0.8 (maximum CO2 solubility of 795 ± 41, 1376 ± 73 and 2949 ± 166 ppm at 100, 200 and 500 MPa, respectively), indicating that dissolved water strongly enhances the solubility of CO2. A similar nonlinear variation of CO2 solubility with xCO2fluid has been observed for rhyolitic melts in which carbon dioxide is incorporated exclusively as molecular CO2 (Tamic et al., 2001). We infer that water species in the melt do not only stabilize carbonate groups as has been suggested earlier but also CO2 molecules.A thermodynamic model describing the dependence of the CO2 solubility in hydrous rhyolitic and dacitic melts on T, P, fCO2 and the mol fraction of water in the melt (xwater) has been developed. An exponential variation of the equilibrium constant K1 with xwater is proposed to account for the nonlinear dependence of xCO2,totalmelt on xCO2fluid. The model reproduces the CO2 solubility data for dacitic melts within ±14% relative and the data for rhyolitic melts within 10% relative in the pressure range 100-500 MPa (except for six outliers at low xCO2fluid). Data obtained for rhyolitic melts at 75 MPa and 850°C show a stronger deviation from the model, suggesting a change in the solubility behavior of CO2 at low pressures (a Henrian behavior of the CO2 solubility is observed at low pressure and low H2O concentrations in the melt). We recommend to use our model only in the pressure range 100-500 MPa and in the xCO2fluid range 0.1-0.95. The thermodynamic modeling indicates that the partial molar volume of total CO2 is much lower in rhyolitic melts (31.7 cm3/mol) than in dacitic melts (46.6 cm3/mol). The dissolution enthalpy for CO2 in hydrous rhyolitic melts was found to be negligible. This result suggests that temperature is of minor importance for CO2 solubility in silicic melts.  相似文献   
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Model identification for hydrological forecasting under uncertainty   总被引:2,自引:2,他引:2  
Methods for the identification of models for hydrological forecasting have to consider the specific nature of these models and the uncertainties present in the modeling process. Current approaches fail to fully incorporate these two aspects. In this paper we review the nature of hydrological models and the consequences of this nature for the task of model identification. We then continue to discuss the history (“The need for more POWER‘’), the current state (“Learning from other fields”) and the future (“Towards a general framework”) of model identification. The discussion closes with a list of desirable features for an identification framework under uncertainty and open research questions in need of answers before such a framework can be implemented.  相似文献   
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The chemical structure of refractory marine dissolved organic matter (DOM) is still largely unknown. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS) was used to resolve the complex mixtures of DOM and provide valuable information on elemental compositions on a molecular scale. We characterized and compared DOM from two sharply contrasting aquatic environments, algal-derived DOM from the Weddell Sea (Antarctica) and terrigenous DOM from pore water of a tropical mangrove area in northern Brazil. Several thousand molecular formulas in the mass range of 300-600 Da were identified and reproduced in element ratio plots. On the basis of molecular elemental composition and double-bond equivalents (DBE) we calculated an average composition for marine DOM. O/C ratios in the marine samples were lower (0.36 ± 0.01) than in the mangrove pore-water sample (0.42). A small proportion of chemical formulas with higher molecular mass in the marine samples were characterized by very low O/C and H/C ratios probably reflecting amphiphilic properties. The average number of unsaturations in the marine samples was surprisingly high (DBE = 9.9; mangrove pore water: DBE = 9.4) most likely due to a significant contribution of carbonyl carbon. There was no significant difference in elemental composition between surface and deep-water DOM in the Weddell Sea. Although there were some molecules with unique marine elemental composition, there was a conspicuous degree of similarity between the terrigenous and algal-derived end members. Approximately one third of the molecular formulas were present in all marine as well as in the mangrove samples. We infer that different forms of microbial degradation ultimately lead to similar structural features that are intrinsically refractory, independent of the source of the organic matter and the environmental conditions where degradation took place.  相似文献   
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Blueschist facies rocks in the Yuli Belt of Taiwan's Central Range record ongoing subduction of the Eurasian plate. We present a prograde Lu–Hf garnet–whole‐rock age of 5.1 ± 1.7 Ma from a retrogressed blueschist in the Yuli Belt. This age is considerably younger than the previously assumed age of 14–8 Ma for high‐pressure metamorphism in the Yuli Belt and represents the youngest Lu–Hf garnet age ever recorded for blueschist facies metamorphism. The age sheds new light on the palaeogeographic origin and exhumation scenario of the Yuli Belt. We propose that the Yuli Belt originated from the ocean–continent boundary of the Chinese passive margin. It was subducted eastward during collision with the Luzon island arc and rapidly exhumed when the forearc lithosphere was removed from above the continental slab by discrete subduction (extraction). This process reduces the pressure above the continental slab and may prompt the ascent of subducted crust into the opening gap. Thus, it can control the exhumation of high‐pressure rocks.  相似文献   
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Groundwater storage, drainage, and interbasin water exchange are common hydrological processes but often difficult to quantify due to a lack of local observations. We present a study of three volcanic mountainous watersheds located in south‐central Chile (~36.9 ° S) in the Chillán volcanic complex (Chillán, Renegado, and Diguillín river basins). These are neighboring basins that are similar with respect to the metrics normally available for characterization everywhere (e.g., precipitation, temperature, and land cover). In a hydrological sense, similar (proportional) behavior would be expected if these catchments would be characterized with this general information. However, these watersheds show dissimilar behavior when analyzed in detail. The surface water balance does not fit for any of these watersheds individually; however, the water balance of the whole system can be explained by likely interbasin water exchanges. The Renegado river basin has an average annual runoff per unit of area on the order of 60–65% less than those of the Diguillín and Chillán rivers, which is contradictory to the hydrological similarity among the basins. To understand the main processes that control streamflow generation, two analyses were performed: (a) basin metrics (land cover, geologic, topographic, and climatological maps) and hydro‐meteorological data analyses and (b) a water balance model approach. The analyses contribute to a plausible explanation for the hydrogeological processes in the system. The soils, topography, and geology of the Chillán–Renegado–Diguillín system favor the infiltration and groundwater movements from the Renegado river basin, mainly to the neighboring Diguillín basin. The interbasin water exchanges affect hydrological similarity and explain the differences observed in the hydrological processes of these three apparently similar volcanic basins. The results highlight the complexity of hydrological processes in volcanic mountainous systems and suggest that a simple watershed classification approach based on widely available data is insufficient. Simple local analyses such as specific flow analysis with a review of the geology and morphology can contribute to a better understanding of the hydrology of volcanic mountainous areas.  相似文献   
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Dissolved organic matter (DOM) was investigated along a gradient across the Subtropical Convergence (STC) off the South Island, New Zealand. Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), excitation emission matrix fluorescence (EEM) spectroscopy, and molecular lignin analysis techniques were used to study this DOM. The analysis revealed a group of compounds found only in the coastal DOM samples, which were also characterized by an elevated terrestrial DOM fluorescence pattern and elevated lignin content if compared to the offshore samples. This group exhibited a high degree of carbon unsaturation, as evident from high double bond equivalence minus oxygen values (DBE-O > 9) and maximum fluorescence intensity. Sulfur-containing molecular formulae for summer DOM samples were much more abundant across the entire transect of the STC compared to winter and exhibited distinctly different hydrogen:carbon and oxygen:carbon elemental ratios, suggesting a possible correlation between biological activity and sulfur compounds. The molecular formulae common to all STC samples were compared with those calculated for DOM extracted from freshwater collected from a stream discharging into Doubtful Sound (West Coast, New Zealand). ESI-FT-ICR-MS measurements undertaken in negative electrospray ionization (ESI?) mode indicated that 30% of the molecular formulae were present in both types of DOM, while in positive ESI mode (ESI+) over 90% of the formulae were present in all samples. Hence, a significant portion of the molecular formulae assigned to the solid-phase extractable DOM pool (SPE-DOM) appear to be identical in oceanic and freshwater samples.  相似文献   
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