Progress and new directions in high temperature calorimetry

Calorimetry at 600–900° C, using Calvet-type microcalorimeters, has provided data in several areas of interest to geology. The best-developed application is solution calorimetry in molten oxide solvents (lead borate, sodium molybdate) to determine the enthalpies of formation of anhydrous silicates and related minerals, the enthalpies of phase transformations and order-disorder reactions, and the enthalpies of mixing in molten salts, glasses, and solid solutions. An attractive feature of the technique is the ability to use rather small samples; ～ 300 mg total often being sufficient for the study of a phase synthesized at high pressure. Current developments include the improvement of precision by careful control of solvent composition and water content, the development of alkali borate or borosilicate solvents for use under atmospheres of controlled oxygen fugacity, and the study of compounds containing fluorine as well as oxygen. In addition, direct-reaction calorimetry at high temperature has been used to study rapid phase transformations and gas-solid reactions. The latter include the oxidation of metals and the thermodynamics of oxides having wide homogeneity ranges, for example wüstite. A recent development is calorimetry at pressures up to 2 kb, using a cold-seal pressure vessel inserted in the calorimeter. Applications include the study of geothermal fluids and, eventually, the study of equilibria involving hydrous phases and water-containing melts and glasses.     

29Si and 1H NMR spectroscopy of high-pressure hydrous magnesium silicates

We present NMR spectroscopic data, obtained by ¹H MAS, ¹H static spin-echo, and ²⁹Si{¹H} CP-MAS techniques, for a series of hydrous magnesium silicate samples synthesized at high pressure. This series includes chondrodite, β-Mg₂SiO₄, and phases A, B, superhydrous B, and E. Phases B and superhydrous B give very narrow ²⁹Si NMR peaks and display the most de-shielded Si^VI chemical shifts yet reported: ?170.4?ppm for B and ?166.6 for superhydrous B. The ¹H NMR spectra of B and superhydrous B confirm the presence of paired hydroxyls, as determined from refinement of the H positions from X-ray diffraction data. The ¹H MAS NMR spectra of phase B contain peaks for the two distinct hydrogen positions, with chemical shifts of +4.7 and +3.3?ppm. The static ¹H spectrum contains a powder pattern characteristic of a strongly coupled hydrogen pair, from which a dipolar coupling constant of 18.6(4)?kHz and inter-hydrogen distance of d(H–H)=1.86(2)?Å were obtained. Superhydrous B appears to give two poorly resolved ¹H MAS peaks, consistent with the presence of two distinct hydrogen pairs in the P2₁ mn crystal structure. Analysis of its spin-echo spectrum gives d(H–H)=1.83(3)?Å, slightly shorter than for phase B. β-Mg₂SiO₄, coexisting with phases B and superhydrous B, appears to give ²⁹Si{¹H} CP-MAS signal, indicating that it contains significant H concentration. The ²⁹Si chemical shifts for phases B, superhydrous B, and chondrodite, together with those reported previously for other Mg-silicates, show a good correlation with structural parameters.     

Vertical structure of hydrophysical characteristics and internal waves near the shelf boundary

Short and high frequency internal waves, propagating through horizontal gradients of temperature formed by long and low-frequency waves, induce vertical transferof heat with effective coefficients 10⁻⁴ – 10⁻³ m²/s and lead to a fine structure formation. Horizontal turbulence with seals of order 100 m produce the same effect in the presence of internal waves. The same is true for other substances, such as salt, oxygen, organic matter. It is suggested that this augmenting of vertical transports due to internal waves is an essential factor for high biological productivity in shelf zones.     

Combining geographic information system, multicriteria evaluation techniques and fuzzy logic in siting MSW landfills

This study presents a methodology for siting municipal solid waste landfills, coupling geographic information systems (GIS), fuzzy logic, and multicriteria evaluation techniques. Both exclusionary and non-exclusionary criteria are used. Factors, i.e., non-exclusionary criteria, are divided in two distinct groups which do not have the same level of trade off. The first group comprises factors related to the physical environment, which cannot be expressed in terms of monetary cost and, therefore, they do not easily trade off. The second group includes those factors related to human activities, i.e., socioeconomic factors, which can be expressed as financial cost, thus showing a high level of trade off. GIS are used for geographic data acquisition and processing. The analytical hierarchy process (AHP) is the multicriteria evaluation technique used, enhanced with fuzzy factor standardization. Besides assigning weights to factors through the AHP, control over the level of risk and trade off in the siting process is achieved through a second set of weights, i.e., order weights, applied to factors in each factor group, on a pixel-by-pixel basis, thus taking into account the local site characteristics. The method has been applied to Evros prefecture (NE Greece), an area of approximately 4,000 km². The siting methodology results in two intermediate suitability maps, one related to environmental and the other to socioeconomic criteria. Combination of the two intermediate maps results in the final composite suitability map for landfill siting.     

Diamond precipitation from ascending reduced fluids in the Kaapvaal lithosphere: Thermodynamic constraints

Previous research has shown that the Kaapvaal lithospheric mantle is generally reduced and characterised by a decreasing redox state with increasing depth. As a consequence, C-O-H fluids in the Kaapvaal lithospheric mantle are dominated by H₂O, CH₄, and C₂H₆. Thermodynamic calculations demonstrate that diamond precipitation from such a fluid during ascend is possible as it is exposed to a more oxidised environment and both CH₄ and C₂H₆ are oxidised. However, the calculations also demonstrate that the diamond precipitation potential from such a fluid decreases when: (1) the mantle is either more reduced or oxidised compared to the Kaapvaal mantle, or (2) the change in temperature with pressure is smaller compared to that of the Kaapvaal mantle. Therefore, the presence of reduced mantle fluid species and a generally decreasing oxygen fugacity with increasing depth do not necessarily warrant diamond precipitation from a rising reduced fluid.     

Transition zone structure under a stationary hot spot: Cape Verde

We report on a two-year seismic deployment in the Cape Verde Islands, one goal of which was to study the upper mantle to determine its structure under a hot spot that is stationary in the hot spot reference frame. We find from analysis of P-to-S receiver functions estimated from broadband seismic recordings that, within uncertainty, the time separation between the 410 and 660 km discontinuities is normal compared to radial earth models. Thus, to exist, even stationary hot spots do not require vertical thermal anomalies from deep melting sources anchored in the lower mantle or at the core–mantle boundary or their anomalies are narrower than ～ 250 km in the upper mantle.     

New data on the palaeobiogeography of Loftusia genus (Foraminiferida). An in situ presence of the genus in eastern Greece (Boeotia)

An Upper Maastrichtian horizon rich in Loftusia is for the first time described in situ in Greece in the province of Boeotia. It is found in a continuous undisturbed carbonate sequence of the eastern Greece platform (Subpelagonian zone) of Maastrichtian–Paleocene age followed by flysch sedimentation. Loftusia is found in a facies reflecting an outer shelf environment, associated with debris of rudists, Orbitoides spp., Siderolites calcitrapoides, Omphalocyclus macroporus, Hellenocyclina beotica, Sulcoperculina sp., and echinoderms. Similar fauna, but without Loftusia, is found in the surrounding levels of Late Maastrichtian age as well. This recovery of the genus in the western part of its distribution area, where it is not as abundant as in the eastern part, is considered significant for the palaeobiogeography of the genus in Tethys Ocean during Late Cretaceous. To cite this article: A. Zambetakis-Lekkas, A. Kemeridou, C. R. Geoscience 338 (2006).     

Monitoring and early warning of the 2012 Preonzo catastrophic rockslope failure

In this paper, we describe the investigations and actions taken to reduce risk and prevent casualties from a catastrophic 210,000 m³ rockslope failure, which occurred near the village of Preonzo in the Swiss Alps on May 15, 2012. We describe the geological predisposition and displacement history before and during the accelerated creep stage as well as the development and operation of an efficient early warning system. The failure of May 15, 2012, occurred from a large and retrogressive instability in gneisses and amphibolites with a total volume of about 350,000 m³, which formed an alpine meadow 1250 m above the valley floor. About 140,000 m³ of unstable rock mass remained in place and might collapse partially or completely in the future. The instability showed clearly visible signs of movements along a tension crack since 1989 and accelerated creep with significant hydromechanical forcing since about 2006. Because the active rockslide at Preonzo threatened a large industrial facility and important transport routes located directly at the toe of the slope, an early warning system was installed in 2010. The thresholds for prealarm, general public alarm, and evacuation were derived from crack meter and total station monitoring data covering a period of about 10 years, supplemented with information from past failure events with similar predisposition. These thresholds were successfully applied to evacuate the industrial facility and to close important roads a few days before the catastrophic slope failure of May 15, 2012. The rock slope failure occurred in two events, exposing a compound rupture plane dipping 42° and generating deposits in the midslope portion with a travel angle of 39°. Three hours after the second rockslide, the fresh deposits became reactivated in a devastating debris avalanche that reached the foot of the slope but did not destroy any infrastructure. The final run-out distance of this combined rock collapse–debris avalanche corresponded to the predictions made in the year 2004.     

Thermodynamic data of lawsonite and zoisite in the system CaO–Al2O3–SiO2–H2O based on experimental phase equilibria and calorimetric work

The enthalpy of drop-solution in molten 2PbO·B₂O₃ of synthetic and natural lawsonite, CaAl₂(Si₂O₇)(OH)₂·H₂O, was measured by high-temperature oxide melt calorimetry. The enthalpy of formation determined for the synthetic material is (_fH^Oxides=-168.7Dž.4 kJ mol^-1, or (_fH⁰₂₉₈=-4,872.5dž.0 kJ mol^-1. These values are in reasonable agreement with previously published data, although previous calorimetric work yielded slightly more exothermic data and optimisation methods resulted in slightly less exothermic values. The equilibrium conditions for the dehydration of lawsonite to zoisite, kyanite and quartz/coesite at pressures and temperatures up to 5 GPa and 850 °C were determined by piston cylinder experiments. These results, other recent phase equilibrium data, and new calorimetric and thermophysical data for lawsonite and zoisite, Ca₂Al₃(SiO₄)(Si₂O₇)O(OH), were used to constrain a mathematical programming analysis of the thermodynamic data for these two minerals in the chemical system CaO-Al₂O₃-SiO₂-H₂O (CASH). The following data for lawsonite and zoisite were obtained: (_fH⁰₂₉₈ (lawsonite)=-4,865.68 kJ mol^-1 , S⁰₂₉₈ (lawsonite)=229.27 J K^-1 mol^-1 , (_fH⁰₂₉₈ (zoisite)=-6,888.99 kJ mol^-1 , S⁰₂₉₈ (zoisite)=297.71 J K^-1 mol^-1 . Additionally, a recalculation of the bulk modulus of lawsonite yielded K=120.7 GPa, which is in good agreement with recent experimental work.