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Large-eddy simulations of a clear convective boundary layer (CBL)and a stratocumulus-topped boundary layer are studied. Bottom-upand a top-down scalars were included in the simulations, and theprinciple of linear superposition of variables was applied toreconstruct the fields of any arbitrary conserved variable.This approach allows a systematic analysis of countergradient fluxesas a function of the flux ratio, which is defined as the ratio betweenthe entrainment flux and the surface flux of the conserved quantity.In general, the turbulent flux of an arbitrary conserved quantityis counter to the mean vertical gradient if the heights where thevertical flux and the mean vertical gradient change sign do notcoincide. The regime where the flux is countergradient is thereforebounded by the so-called zero-flux and zero-gradient heights. Becausethe vertical flux changes sign only if the entrainment flux has anopposite sign to the surface flux, countergradient fluxes arepredominantly found for negative flux ratios. In the CBL the fluxratio for the virtual potential temperature is, to a good approximation,constant, and equal to -0.2. Only if the moisture contribution to thevirtual potential temperature is negligibly small will the flux ratio forthe potential temperature be equal to this value. Otherwise, theflux ratio for the potential temperature can have any arbitrary(negative) value, and, as a consequence, the fluxes for thepotential temperature and the virtual potential temperature willbe countergradient at different heights. As a practical application ofthe results, vertical profiles of the countergradient correction termfor different entrainment-to-surface-flux ratios are discussed.  相似文献   
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The structures of sodium silicate and aluminosilicate glasses quenched from melts at high pressure (6-10 GPa) with varying degrees of polymerization (fractions of nonbridging oxygen) were explored using solid-state NMR [17O and 27Al triple-quantum magic-angle spinning (3QMAS) NMR]. The bond connectivity in melts among four and highly coordinated network polyhedra, such as [4]Al, [5,6]Al, [4]Si, and [5,6]Si, at high pressure is shown to be significantly different from that at ambient pressure. In particular, in the silicate and aluminosilicate melts, the proportion of nonbridging oxygen (NBO) generally decreases with increasing pressure, leading to the formation of new oxygen clusters that include 5- and 6-coordinated Si and Al in addition to 4-coordinated Al and Si, such as [4]Si-O-[5,6]Si, [4]Si-O-[5,6]Al and Na-O-[5,6]Si. While the fractions of [5,6]Al increase with pressure, the magnitude of this increase diminishes with increasing degrees of ambient-pressure polymerization under isobaric conditions. Incorporating the above structural information into models of melt properties reproduces the anomalous pressure-dependence of O2− diffusivity and viscosity often observed in silicate melts.  相似文献   
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Solubility mechanisms of water in depolymerized silicate melts quenched from high temperature (1000°-1300°C) at high pressure (0.8-2.0 GPa) have been examined in peralkaline melts in the system Na2O-SiO2-H2O with Raman and NMR spectroscopy. The Na/Si ratio of the melts ranged from 0.25 to 1. Water contents were varied from ∼3 mol% and ∼40 mol% (based on O = 1). Solution of water results in melt depolymerization where the rate of depolymerization with water content, ∂(NBO/Si)/∂XH2O, decreases with increasing total water content. At low water contents, the influence of H2O on the melt structure resembles that of adding alkali oxide. In water-rich melts, alkali oxides are more efficient melt depolymerizers than water. In highly polymerized melts, Si-OH bonds are formed by water reacting with bridging oxygen in Q4-species to form Q3 and Q2 species. In less polymerized melts, Si-OH bonds are formed when bridging oxygen in Q3-species react with water to form Q2-species. In addition, the presence of Na-OH complexes is inferred. Their importance appears to increase with Na/Si. This apparent increase in importance of Na-OH complexes with increasing Na/Si (which causes increasing degree of depolymerization of the anhydrous silicate melt) suggests that water is a less efficient depolymerizer of silicate melts, the more depolymerized the melt. This conclusion is consistent with recently published 1H and 29Si MAS NMR and 1H-29Si cross polarization NMR data.  相似文献   
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Mossbauer spectroscopy has been used to determine the redox equilibria of iron and structure of quenched melts on the composition join Na2Si2O5-Fe2O3 to 40 kbar pressure at 1400° C. The Fe3+/ΣFe decreases with increasing pressure. The ferric iron appears to undergo a gradual coordination transformation from a network-former at 1 bar to a network-modifier at higher (≧10 kbar) pressure. Ferrous iron is a network-modifier in all quenched melts. Reduction of Fe3+ to Fe2+ and coordination transformation of remaining Fe3+ result in depolymerization of the silicate melts (the ratio of nonbridging oxygens per tetrahedral cations, NBO/T, increases). It is suggested that this pressure-induced depolymerization of iron-bearing silicate liquids results in increasing NBO/T of the liquidus minerals. Furthermore, this depolymerization results in a more rapid pressure-induced decrease in viscosity and activation energy of viscous flow of iron-bearing silicate melts than would be expected for iron-free silicate melts with similar NBO/T.  相似文献   
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