Viscosity and configurational entropy of silicate melts

With the configurational entropy theory of relaxation processes of Adam and Gibbs (1965), one predicts that the viscosity depends on temperature according to log $\text{η = A}{}_{\mathrm{e}}\text{+}\text{B}{}_{\mathrm{e}}\text{TS}{}_{\mathrm{<mtext>conf</mtext>}}$, where S_conf is the configurational entropy of the liquid. Thermochemical calculations of S_conf performed for some mineral compositions show the importance of non-configurational contributions to the entropy differences between amorphous and crystalline phases. Except for the case of SiO₂, the available thermodynamic data indicate that the above equation for viscosity accounts quantitatively for the experimentally determined temperature dependence of the viscosity of silicate melts. The Adam and Gibbs theory also provides a simple rationale for the non linear variation of the logarithmic viscosity with composition in mixed alkali silicate liquids at low temperatures, the minimum of viscosity resulting from the contribution of the entropy of mixing to S_conf.     

Density calculations for silicate liquids. I. Revised method for aluminosilicate compositions

Equations are developed for calculating the density of aluminosilicate liquids as a function of composition and temperature. The mean molar volume at reference temperature T_r, is given by $\text{V}{}_{\mathrm{r}}\text{= ∑X}{}_{\mathrm{i}}\text{V}\text{?}{}^{\mathrm{o}}{}_{\mathrm{i}}\text{+ X}{}_{\mathrm{A}}\text{V}\text{?}{}^{\mathrm{o}}{}_{\mathrm{A}}$, where the summation is taken over all oxide components except A1₂O₃, X stands for mole fraction, terms are constants derived independently from an analysis of volume-composition relations in alumina-free silicate liquids, and $\text{V}\text{?}{}^{\mathrm{o}}{}_{\mathrm{A}}$ is the composition-dependent apparent partial molar volume of Al₂O₃. The thermal expansion coefficient of aluminosilicate liquids is given by $\text{α = ∑X}{}_{\mathrm{i}}\text{}\text{?}\text{ga}{}_{\mathrm{i}}{}^{\mathrm{o}}\text{+ X}{}_{\mathrm{A}}\text{}\text{?}\text{ga}{}_{\mathrm{A}}{}^{\mathrm{o}}$, where $\text{}\text{?}\text{ga}{}_{\mathrm{i}}{}^{\mathrm{o}}$ terms are constants independent of temperature and composition, and $\text{}\text{?}\text{ga}{}^{\mathrm{o}}{}_{\mathrm{A}}$ is a composition-dependent term representing the effect of Al₂O₃ on the thermal expansion. Parameters necessary to calculate the volume of silicate liquids at any temperature T according to V(T) = V_rexp[α(T-T_r)], where T_r = 1400°C have been evaluated by least-square analysis of selected density measurements in aluminosilicate melts. Mean molar volumes of aluminosilicate liquids calculated according to the model equation conform to experimentally measured volumes with a root mean square difference of 0.28 $\text{cc}\text{mole}$ and an average absolute difference of 0.90% for 248 experimental observations. The compositional dependence of $\text{V}\text{?}{}^{\mathrm{o}}{}_{\mathrm{A}}$ is discussed in terms of several possible interpretations of the structural role of Al³⁺ in aluminosilicate melts.     

Thermochemistry and melting properties of basalt

The heat capacities of the liquid, glassy and crystalline phases of an alkali basalt have been determined from relative enthalpies measured between 400 and 1,800 K. Values given by available models of calculation generally agree to within 2% of these results. As derived from the new data and the enthalpy of vitrification measured at 973 K by oxide-melt drop solution calorimetry for the same sample, the enthalpy of fusion of this basalt increases from 15.4 kJ/mol at 1,000 K to 33.6 kJ/mol at 1,800 K. Comparisons between the enthalpies of fusion of basalt and model compositions confirm the small magnitude of the enthalpy of mixing between the molten mineral components of the liquids. Minor variations in the chemical composition have only a small effect in the heat capacity and the enthalpy of melting of basalt. The enthalpies of formation at 298 K from the oxides of the crystallized and glass phases of this alkali basalt are −112.2 and −98.5 kJ/mol, respectively, for a gram formula weight based on one mole of oxide components.     

Wet Snow Avalanche Deposits in the French Alps: Structure and Sedimentology

We analyse the morphology and sedimentology of 25 dirty snow avalanche deposits in the French Alps. The deposits typically have either a snow-ball structure or a massive structure with sliding planes. The snow balls show a longitudinal and a vertical sorting that reflects a sieve effect, similar to that observed in other rapid inertial granular flows. The massive type results from snow compaction when the avalanche is channelled by a gully or when it reaches the distal part of the scree. Velocity decrease and compaction limit the deformation to a zone at the base of the snow mass and cause the formation of distinctive sliding planes. These appear as smooth recrystallised surfaces due to local melt from frictional heating. The flow can be assimilated to a frictional granular flow. No systematic variation of size and shape of the rock debris has been observed along the profiles in both types of deposit. The distribution of rock debris and its fabric suggest that the clasts are transported passively and do not undergo any sorting during displacement. Snow melt after avalanching causes a redistribution of rock debris particularly when the snow thickness is important. This redistribution does not generate new sedimentological characteristics such as enhanced sorting or fabric.     

Fluid composition and evolution in coesite-bearing rocks (Dora-Maira massif,Western Alps): implications for element recycling during subduction

Fluid inclusions and F, Cl concentration of hydrous minerals were analysed in the coesite-pyrope quartzite, the interlayered jadeite quartzite and their country-rock gneiss from the Dora-Maira massif using a combination of microthermometry, Raman spectrometry, synchrotron X-ray microfiuorescence and electron microprobe analysis. Three populations of fluid inclusions were recognized texturally and can be related to distinct metamorphic stages. A low-salinity aqueous fluid occurs in the retrogressed country gneiss and as late secondary inclusions in jadeite quartzite and chloritized pyrope. An earlier secondary population is found in matrix quartz of the jadeite- and pyro-pe-quartzites. This population can be related to the early decompression and so to incipient breakdown of garnet into phlogopite-bearing assemblages. The inclusion fluid is highly saline (up to 84 wt% equivalent NaCl) and contains Na, Ca, Fe, Cu and Zn as major cations. In pyrope quartzite, additional K was found in these brines, which locally coexist with CO₂-rich inclusions. The oldest fluid inclusions are preserved in kyanite grains included in fresh pyrope and in pyrope itself. In pyrope, all inclusions have decrepitated and contain magnesite, an Mg-phosphate, sheet-silicate(s), a chloride and an opaque phase, with no fluid preser ved. In contrast, the kyanite inclusions in pyrope preserve primary H₂O-CO₂ low-salinity fluid inclusions, probably owing to the low compressibility of the kyanite inclusions and host garnet. In spite of in-situ re-equilibration, these inclusions can be interpreted as relics of the dehydration fluid that attended pyrope growth. These correlations between textural and chemical fluid inclusion data and metamorphic stages are consistent with the fluid composition calculated from the halogen content of different generations of phlogopite and biotite. The preservation of different fluid compositions, both in time and space, is evidence for local control and possibly origin of the fluids, in agreement with isotopic data. These results, in particular the absence of CO₂ in the jadeite quartzite, are best interpreted in terms of a fluid-melt system evolution. With increasing metamorphism, partitioning of H₂O, Na, Ca, Fe and heavy metals into melt (jadeite quartzite) and Mg, Na/K, F, CO₂ and P(?) into a residual aqueous fluid can account for depletion in Na, Ca and Fe of the pyrope quartzite. During the retrograde path, a _{H 2 O} rose as melt crystallized, generating the two populations of hypersaline and water-rich fluids that were highly reactive to pyrope. The process of fluid-melt interaction envisioned here coupled with models of melt extraction in subduction zones provides an attractive opportunity for the instantaneous ( < 1 Ma) and selective transport of elements between a downgoing slab and the overlying mantle wedge.     

A preliminary investigation of strong-motion data from the French Antilles

Strong-motion networks have been operating in the Caribbean region since the 1970s, however, until the mid-1990s only a few analogue stations were operational and the quantity of data recorded was very low. Since the mid-1990s, digital accelerometric networks have been established on islands within the region. At present there are thought to be about 160 stations operating in this region with a handful on Cuba, 65 on the French Antilles (mainly Guadeloupe and Martinique), eight on Jamaica, 78 on Puerto Rico (plus others on adjacent islands) and four on Trinidad.After briefly summarising the available data from the Caribbean islands, this article is mainly concerned with analysing the data that has been recorded by the networks operating on the French Antilles in terms of their distribution with respect to magnitude, source-to-site distance, focal depth and event type; site effects at certain stations; and also with respect to their predictability by ground motion estimation equations developed using data from different regions of the world. More than 300 good quality triaxial acceleration time-histories have been recorded on Guadeloupe and Martinique at a large number of stations from earthquakes with magnitudes larger than 4.8, however, most of the records are from considerable source-to-site distances. From the data available it is found that many of the commonly-used ground motion estimation equations for shallow crustal earthquakes poorly estimate the observed ground motions on the two islands; ground motions on Guadeloupe and Martinique have smaller amplitudes and are more variable than expected. This difference could be due to regional dependence of ground motions because of, for example, differing tectonics or crustal structures or because the ground motions so far recorded are, in general, from smaller earthquakes and greater distances than the range of applicability of the investigated equations.     

Mid-Holocene to present-day evolution of the Indian monsoon in transient global simulations

The low-frequency evolution of Indian rainfall mean-state and associated interannual-to-decadal variability is discussed for the last 6000 years from a multi-configuration ensemble of fully coupled global transient simulations. This period is marked by a shift of Indian Summer Monsoon Rainfall (ISMR) distribution towards drier conditions, including extremes, and a contraction of the rainy season. The drying is larger in simulations with higher horizontal resolution of the atmosphere and revised land surface hydrology. Vegetation–climate interactions and the way runoff is routed to ocean modulate the timing of the monsoon onset but have negligible effects on the evolution of seasonal rainfall amounts in our modeling framework in which carbon cycling is always active. This drying trend is accompanied by changes in ISMR interannual-to-decadal variability decreasing over north and south India but increasing over central India (20°–25° N). The ISMR interannual-to-decadal variability is decomposed into six physically consistent regimes using a clustering technique to further characterize its changes and associated teleconnections. From 6 to 3.8 kyr bp, the century-to-century modulations in the frequency of occurrence associated to the regimes are asynchronous between the simulations. Orbitally-driven trends can only be detected for two regimes over the whole 6–0 kyr bp period. These two regimes reflect increased influence of ENSO on both ISMR and Indian Ocean Dipole as the inter-hemispheric energy gradient weakens. Severe long-term droughts are also shown to be a combination of long-term drying and internally generated low-frequency modulations of the interannual-to-decadal variability.

     

Heat capacity of liquid silicates: new measurements on NaAlSi3O8 and K2Si4O9

Drop calorimetric measurements of H_T-H₂₇₃ are reported for glassy and liquid albite and potassium tetrasilicate for the temperature interval 600–1500 K. Analysis of these observations as well as data for 13 other stable and supercooled silicate liquids suggests strongly that the isobaric heat capacities of stable and supercooled liquids are equal and thus temperature independent. Available evidence indicates that the isochoric heat capacities of liquid alkali silicates are also temperature independent within present experimental uncertainties.