Calorimetry of silicate melts at 1773 K: measurement of enthalpies of fusion and of mixing in the systems diopside-anorthite-albite and anorthite-forsterite

Transposed-temperature-drop calorimetry, using a Setaram HT 1500 calorimeter, was used to study directly the melting at 1773 K of mixtures of crystalline albite, anorthite, and diopside and of anorthite and forsterite. The enthalpy of albite at 1000–1773 K, starting with both crystalline and glassy samples, was also measured. The results confirm previously measured enthalpies of fusion of albite, diopside and anorthite (Stebbins et al. 1982, 1983; Richet and Bottinga 1984,1986). The new results use thermochemical cycles which completely avoid the glassy state by transforming crystals directly to melts. The enthalpy of fusion of forsterite is estimated to be 89±12 kJ/mol at 1773 K and 114±20 kJ/mol at its melting point of 2163 K. The data allow semiquantitative evaluation of heats of mixing in the molten silicates. Along the Ab-An join, enthalpies of mixing in the liquid at 773 K are the same or somewhat more negative than those in the glass at 986 K, whereas along Ab-Di and An-Di, enthalpies of mixing in the liquid are distinctly more positive than in the glass. These differences correlate with excess heat capacities in the liquids suggested by Stebbins et al. (1984).     

Transition enthalpies and entropies of high pressure zinc metasilicates and zinc metagermanates

The enthalpies of transition at T= 298 K between zinc metasilicate assemblages, measured by molten oxide solution calorimetry, are:

Phase equilibrium and calorimetric study of the transition of MnTiO3 from the ilmenite to the lithium niobate structure and implications for the stability field of perovskite

The phase boundary between MnTiO₃ I (ilmenite structure) and MnTiO₃ II (lithium niobate structure) has been determined by analysis of quench products from reversal experiments in a cubic anvil apparatus at 1073–1673 K and 43–75 kbar using mixtures of MnTiO₃ I and II as starting materials. Tight brackets of the boundary give P(kbar)=121.2−0.045 T(K). Thermodynamic analysis of this boundary gives ΔH^o=5300±1000 J·mol⁻¹, ΔS^o = 1.98 ±1J·K⁻¹· mol⁻¹. The enthalpy of transformation obtained directly by transposed-temperature-drop calorimetry is 8359 ±2575 J·mol⁻¹. Possible topologies of the phase relations among the ilmenite, lithium niobate, and perovskite polymorphs are constrained using the above data and the observed (reversible with hysteresis) transformation of II to III at 298 K and 20–30 kbar (Ross et al. 1989). The observed II–III transition is likely to lie on a metastable extension of the II–III boundary into the ilmenite field. However the reversed I–II boundary, with its negative dP/ dT does represent stable equilibrium between ilmenite and lithium niobate, as opposed to the lithium niobate being a quench product of perovskite. We suggest a topology in which the perovskite occurs stably at low T and high P with a triple point (I, II, III) at or below 1073 K near 70 kbar. The I–II boundary would have a negative P-T slope while the II–III and I–III boundaries would be positive, implying that entropy decreases in the order lithium niobate, ilmenite, perovskite. The inferred positive slope of the ilmenite-perovskite transition in MnTiO₃ is different from the negative slopes in silicates and germanates. These thermochemical parameters are discussed in terms of crystal structure and lattice vibrations.     

Energetics of radiation damage in natural zircon (ZrSiO4)

Transposed temperature drop calorimetry at 1000 °C was performed on natural zircons (ZrSiO₄) from Sri Lanka that were partially to completely metamict due to α-decay event damage (0.06 to 11.7×10¹⁵ α-decay events/mg). The enthalpy of annealing at room temperature (ΔH_anneal) varies sigmoidally as a function of radiation dose. ΔH_anneal reaches a saturation plateau at radiation doses greater than 5×10¹⁵ α-decay events/mg. The annealing of several samples to a crystalline structure with broadened diffraction peaks does not significantly affect the enthalpy of annealing. The large magnitude of the enthalpy of annealing plateau, ?59±3 kJ/mol, suggests that the damage to the structure is pervasive on the scale of Angstroms, consistent with the loss of mid-range order characteristic of a glass. The energetics are consistent with, but do not require, chemical heterogeneity caused by micro-domains of amorphous SiO₂-rich and ZrO₂-rich regions in the metamict state.     

Distribution and migrations of the prawnPalaemon longirostris in the Mira River estuary (southwest Portugal)

Palaemon longirostris was sampled monthly at 12 sites in the Mira River estuary (southwest Portugal) from October 1990 to September 1991. Animals were counted, measured, and sexed. The estuarine distribution of prawns appeared to follow the salinity displacement, the animals being found at river stations during summer and autumn when saline encroachment up the estuary was greater. During winter and spring when freshwater input from the river was greatest, and thus moving the salinity gradient toward the mouth, the prawns migrated downstream to brackish areas. Ovigerous females were collected only from estuarine areas (January to August), suggesting that reproduction does not take place in freshwater habitats. Higher percentages of females than males were generally observed. Females, particularly ovigerous ones, were larger than males.     

Variation among fossil chironomid assemblages in surficial sediments of Bodensee-Untersee (SW-Germany): implications for paleolimnological interpretation

In paleolimnology, subfossil head capsules of chironomids play an important role as ecological indicators of lake history. It is important to determine, therefore, whether fossil assemblages are representative of former biocoenoses. There is evidence that headcapsules washed in from other places can make up a significant percentage of the total. As interpretations are usually drawn from the examination of a single core, it is of special interest to know whether a fossil assemblage of a single site properly reflects limnological conditions of the whole lake. This study examined the taxonomic distribution of subfossil chironomids in the surficial sediments of the Bodensee-Untersee, with the aim of assessing the variability in chironomid assemblages. Apparently, most of the head capsules of the profundal fossil assemblages in the Untersee had been washed in from the littoral zone or from the slope. Although the Bodensee-Untersee is a rather large lake, variability is surprisingly low among all samples. Therefore a correct interpretation from a single core may be possible.     

Direct measurements of latent heat during crystallization and melting of a ugandite and an olivine basalt

Step-scanning calorimetric measurements using a Setaram HT1500 calorimeter were performed between 800 and 1400°C on two natural samples: a ugandite from the East African rift and an olivine basalt from the western Mexican arc. Our measurements provide the first in-situ quantitative assessment of enthalpy during melting of initially crystalline natural samples. The distribution of latent heat across the liquidus-solidus intervals of the two samples is distinctly different, reflecting significant variation in the sequence and abundance of mineral phases during melting (clinopyroxene and leucite in the ugandite; olivine, clinopyroxene, and plagioclase in the basalt). Our data further indicate that the common assumption of a uniform distribution of latent heat across the liquidus-solidus interval of a magma is a reasonable approximation for the olivine basalt, but is grossly in error for the ugandite. This is due to cotectic precipitation of leucite and clinopyroxene, leading to a large, disproportionate release of latent heat early in the crystallization sequence. The implication for the thermal history of a crystallizing ugandite magma is that therate of heat loss during conductive cooling will unitially be more rapid than the average rate. The net result will be to produce lower magmatic temperatures after a given cooling interval relative to models assuming a uniform release of latent heat. An additional series of scanning calorimetric experiments were performed at variable rates (1,2 and 3°/min) to evaluate the role of kinetics on the distribution of enthalpy during both melting and crystallization of the ugandite and olivine basalt. The results indicate that clinopyroxene is the most important mineral phase in controlling the shapes of the enthalpy profiles during cooling; this is due to its large enthalpy of fusion and its tendency for sluggish nucleation, followed by rapid crystallization at temperatures that vary with cooling rate. The resolution of the calorimeter (in terms of heat detected per unit time) is also important in determining the shapes of theobserved enthalpy profiles during these rapid scans. Estimates based on the observed calorimetric signal associated with melting of olivine, and the lack of a calorimetric signal during melting of leucite, combined with known enthalpies of fusion for the two phases, indicate detection limits of approximately 0.6–1.2 kJ per 5 min increments.     

A thermochemical study of glasses and crystals along the joins silica-calcium aluminate and silica-sodium aluminate

Enthalpies of solution in molten 2PbO · B₂O₃ at 985 K are reported for series of glasses xCa_0.5AlO₂-(1?x)SiO₂ (O ≤ x ≤ 0.99) and xNaAlO₂-(1?x)SiO₂ (0 ≤ x ≤ 0.56). The data are compared to values for the corresponding crystalline aluminosilicates and to preliminary data for systems containing KAlO₂ and Mg_0.5AlO₂. The enthalpies of mixing of glasses become more exothermic with increasing basicity of the mono- or divalent oxide. The tendency toward immiscibility on the silica-rich side, indicated by the shape of the heat of mixing curve between x = 0 and x = 0.4, is pronounced in the calcium aluminate system, but not in the sodium aluminate system. The shape of the heat of mixing curve, which is roughly symmetrical about x = 0.5, can be rationalized in terms of glass structure by considering essentially random substitution of Si and Al on a continuous three dimensional tetrahedral framework, with stabilization arising from electrostatic interactions between aluminum and the nonframework cation balancing the destabilizing effects arising from perturbation of the aluminosilicate framework by the nonframework cation. These trends are consistent with the variation of physical properties of aluminosilicate melts.     

Derivation Of Refractive Index And Temperature Gradients From Optical Scintillometry To Correct Atmospherically Induced Errors For Highly Precise Geodetic Measurements

Refraction effects of optical beams are generally caused by an inhomogeneous propagation medium and are a major source of systematic errors in the precise optical determination of angles and distances in the atmospheric surface layer. In this contribution a method for deriving vertical temperature and refractive index gradients from optical scintillation is presented. Knowledge of these gradients is required for the compensation of atmospherically induced errors for highly precise terrestrial geodetic measurements, like direct transfer and levelling. The advantage of the present optical method is, that temperature and refractive index gradients can be derived as line-averaged values over the propagation path, which is not possible by meteorological point measurements. Field observations have been carried out with a displaced-beam scintillometer over flat terrain and under different atmospheric conditions in order to verify this method. The experiments show, that this method allows to derive accurate correction values for precise terrestrial geodetic measurements.