Test of the vibrational modelling for the λ-type transitions: Application to the α-β quartz transition

Vibrational modelling is at the present time the only known way to predict the heat capacities of the Earth's mantle minerals at high-pressure and high-temperature. To test the validity of this method for λ-type transitions, we have applied it to the α-β quartz transition (T ₀=846±1 K). Raman spectra of quartz were recorded up to 900 K. Measured frequency shifts of the α-quartz Raman modes were then used in conjunction with available high-pressure Raman data to calculate intrinsic mode anharmonicity, through the parameter a _i=(?Lnv_i/?T)_v. Vibrational modelling of the heat capacity at constant volume, Cv, and at constant pressure, Cp, including anharmonic corrections deduced from the a _i parameters, are compared to experimental data. Taking into account the soft-mode associated to the α-β quartz transition, the model reproduces the excess of Cp related to the transition. Then, this study confirms that detecting a soft-mode from vibrational data allows one to predict λ-type transitions. However, when modelling the thermodynamic properties, the contribution of a soft-mode cannot be established from spectroscopic data. Therefore, one needs first to determine this contribution in order to predict the heat capacities of Earth's mantle minerals displaying λ-type transitions. In α-quartz, this contribution has been determined as 0.007% of the total number of the optic modes in the model of the density of states.     

Geothermobarometry in albite-garnet orthogneisses: A case study from the Gran Paradiso nappe (Western Alps)

The aim of this paper is to estimate syntectonic P-T conditions within albite- and garnet-bearing orthogneisses. These rocks are generally characterized by the assemblage quartz + albite + biotite + phengite + CaFe-garnet + epidote + titanite. Garnet contains up to 55 mole per cent of grossular. K-feldspar is a relict magmatic phase.

P-T conditions are estimated using several independent methods. First, it is shown that exchange reactions based on the Fe---Mg partitioning between garnet and biotite or garnet and phengite cannot be used to estimate temperatures in these rocks, due to the high grossular content of garnet. Second, maximum and minimum pressures are constrained, respectively, by the occurrence of albite instead of jadeite + quartz and by the assemblage phengite + biotite + quartz. Third, phase equilibria in albite- and garnet-bearing metagranites are modelled in the system K₂O---CaO---FeO---Al₂O₃---SiO₂---H₂O. Equilibrium curves are calculated for the observed phase compositions. Uncertainties in P-T estimates mainly result from the choice of appropriate non-ideal solution models for the garnet.

An application is developed for granites from the Gran Paradiso nappe (Western Alps). These granites show an heterogeneous deformation of Alpine age expressed by mylonitic shear zones cutting across weakly deformed domains. Estimated P-T conditions for the synkinematic assemblages are 10–16 kbar at 550±50°C.     

Phase transformations and inherited lattice preferred orientations: implications for seismic properties

In phase transitions via either the martensitic (diffusionless shear) or nucleation and growth mechanism a specific orientation relationship may exist between the two phases. In cases where the orientation relationship is known, the lattice preferred orientation (LPO) inherited by the new phase may be calculated from the LPO of the old phase. The method of calculation is presented in a form suitable for the spherical harmonic method of texture analysis using the orientation distribution function (ODF). Examples are presented for the -β-quartz, calcite-aragonite, orthopyroxene-clinopyroxene and olivine-spinel transformations.

The seismic properties of the transformed and untransformed phases are calculated from the ODF and the single crystal elastic constants. In particular the -β quartz transformation is considered in detail. The quartz polycrystal is very anisotropic in the alpha field (V_p anisotropy coefficient, A = 8.1%) and almost isotropic in the β-field (A = 2.1%). The transition is accompanied by V_p velocity increase of 0.6 km/s. In the other example discussed, olivine-β-spinel, there is also a decrease in V_p anisotropy coefficient from 11.1% (olivine) to 4.0% (β-spinel). The estimate of the volume fraction of olivine at the 400 km discontinuity (associated with this phase transition) is shown to depend on the direction of wave propagation.     

Calculated mineral equilibria in the greenschist-blueschist-eclogite facies in Na2O−FeO−MgO−Al2O3−SiO2−H2O

The new, greatly expanded internally-consistent dataset of Holland and Powell includes thermodynamic data for a wide range of mineral end-members in common rock-forming minerals, in particular, including FeMg_-1 substitutions in glaucophane, garnet, chloritoid and carpholite, and FeMg_-1 and MgSiAl_-1Al_-1 substitutions in talc and chlorite. Moreover, we have the uncertainties and correlations for these data. With the data, we have calculated the full pressure-temperature phase diagram for the system Na₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (NFMASH) for quartz (or coesite) and H₂O in excess, in the range 300°–800°C and 5–50 kbars. By solving the set of non-linear equations formed by the equilibrium relationships for an independent set of equations between the end-members in an assemblage in NFMASH, the compositions of the minerals (and PT) can be calculated. Thus the changes in MgSiAl_-1Al_-1 along NMASH reactions, and FeSiAl_-1Al_-1 along NFASH reactions, are calculated, and the changes in FeMg_-1 and MgSiAl_-1Al_-1 along NFMASH reactions are calculated. From this information it is straightforward to generate PT diagrams for specific rock compositions. Mineral assemblages and mineral compositional changes in the phase diagram are discussed in relation to greenschist, blueschist and eclogite facies assemblages in metapelitic rocks. It is found that the correspondence between the predictions of the phase diagrams and the observations on rocks is remarkably good. When semiquantitative extensions of the phase diagram to include Ca(MgFe)_-1, NaSiCa_-1Al_-1, Fe³⁺Al_-1 and KNa_-1 substitutions are taken into account the agreement is essentially complete.     

Ground variation of radon 222 for location of hidden structural features. Example of the south of France (Alpes Maritimes)

We report two examples from the south of the French Alps, showing that radon emanation monitored by alpha-sensitive film may be used to locate certain discrete structural features revealed in data collected by remote sensing from a satellite. The variations observed in our data, over a period of several months, are in accordance with atmospheric changes and might correlate with local seismic activity when the detectors are located directly above structural fractures and the magnitude of the seismic event is greater than 2.     

Depositional mechanics of turbulent nuées ardentes (surges) from their grain sizes

The ability of turbulent nuées ardentes (surges) to transport coarse pyroclasts has been questioned on the basis that settling velocities of coarse fragments in the deposits are much too high for them to have been supported by turbulence in a dilute gas suspension. A computer model is used to evaluate the settling velocity of pyroclasts in suspensions of varying concentration and temperature. Since suspension of grains in low-concentration surges occurs if the shear velocity exceeds the settling velocity, the shear velocities related to the 16th and 84th percentiles, and the mean of the grain-size distribution are compared in surge deposits of the Vulsini, with the shear velocity necessary to move the coarsest grain on the bed surface (the Shields criterion). The results show that the settling velocities do not vary significantly in gaseous suspensions having volume concentrations lower than 15%, and that an increase in concentration to 25% is not sufficient to decrease the settling velocity of the coarser fraction, if it represents flow shear velocity. It is shown that the settling velocity of the mean grain size (M _z ) best depicts the shear velocity of a dilute turbulent suspension. Applying the results to the May 1902 paroxysmal nuées ardentes of Mount Pelée shows that the estimated mean velocities are well within the observed velocities, and sufficient to support all the clasts in dilute, turbulent suspensions.     

Carboxylic monoacids in the air of mayombe forest (Congo): Role of the forest as a source or sink

In the tropical rain forests of the Congo during the dry season, from June to September 1987, carboxylic acid partial pressures (P _gas) in the air above the canopy, at ground level, and at the boundary layer, were estimated from water samples such as fog and rainwater. The concentrations of these acids were also measured in the sap of tree leaves. Tree leaves act as a sink or as a source if the acid P _gas is greater of lower than the acid concentrations in molecular form in sap. For each of these soluble gases, there is a value of P _gas where the exchange is nul. This is called the compensation point. Values of the compensation point for some tree leaves were evaluated according to Henry's law. Henry's law coefficients at ppm levels were redetermined for formic (HCOOH), acetic (CH₃COOH), propionic (CH₃CH₂COOH), and isobutyric (CH₃CH(CH₃)COOH) acids.By comparison of P _gas and compensation points, it is concluded that the forest was a potential source for these acids. The soil-or the litter-acts as a significant source of a carboxylic acid of C₃ or C₄ atoms in the aliphatic chain. This carboxylic acid, not yet fully characterized, could play an important role in the rain acidity in forested zones of the equatorial areas.The direct emission of these carboxylic acids by vegetation was the main source in the boundary layer above the forest. The average emissions were 3.1×10⁹, 7.8×10⁹, and 8.4×10⁹ molecules cm^-2 s^-1 for HCOOH, CH₃COOH, and CH₃CH₂COOH, respectively. The savanna is an exogenous source of HCOOH and CH₃CH₂COOH during moderately rainy days for 30% of the time. The ozonolysis of isoprene seems to be a small source of HCOOH.     

The African rain forest vegetation and palaeoenvironments during late quaternary

This review paper presents first the main pollen results on the vegetation history of the rain forest during the late Quaternary.- The Lake Bosumtwi record (Ghana) shows the disappearance of rain forest from the base of the core (ca. 28 000 yr BP) to ca. 9000 yr BP. During this time interval the vegetation was of montane type with sparse clumps of trees. There is synchronism between montane vegetation disappearance and rain forest reappearance. This phenomenon occurred abruptly around 9000 yr BP.- The Lake Barombi Mbo record (West Cameroon) shows clearly that from ca. 24 000 yr BP until the present time, rain forest persisted with limited variations, and thus, this area represents a refuge area.From these data and other, one concludes that Afromontane vegetation extended to lowland during cool and humid phases.Other palaeoenvironmental data were obtained by diverse geological analyses of the lacustrine sediments. For Bosumtwi, the relatively precise reconstruction of lake-level fluctuations permitted several palaeoclimatic interpretations for the main Holocene phases.For Barombi Mbo, the evolution of total organic carbon (TOC) and total nitrogen (TON) seems to be related mainly to temperature evolution. By comparison with present-day mountain environments, TOC and TON increase in cool environments, but decrease when warmth and humidity increase, as during Holocene time, because the recycling processes speed up in the topsoil. For the same period the alteration of the soils in the catchment produced a strong increase of kaolinite. All these change intervened ca. 9500 yr BP, which is a key date in tropical Africa.In conclusion, climatic correlations between equatorial and dry north tropical Africa illustrate how changes in the forest block must have important effects on adjacent climatic zones.     

Plio-Quaternary geodynamic evolution of a segment of the Peruvian Andean Cordillera located above the change in the subduction geometry: the Cuzco region

The Cuzco region, which is located above a change in subduction geometry, appears to be characterized by a variable Plio-Quaternary tectono-sedimentary evolution essentially located along the major fault system that separates the High Plateaux from the Eastern Cordillera. After the higher surface formation of the High Plateaux, a set of Neogene basins were filled by Miocene “ fluvio-torrential” series and by Plio-Pleistocene fluvio-lacustrine deposits. The Neogene series have been affected by compressional tectonic forces attributed to the Late Miocene. This compression is followed by roughly E-W trending syn-sedimentary extensional tectonics attributed to the Pliocene; it is related to reactivation of the pre-existing major faults, basin evolution, and volcanic activity concentrated along the faults. In the Early Pleistocene, fluvio-lacustrine deposits are affected by syn- and post-sedimentary compressional tectonism it is characterized by shortening that trends both N-S and E-W and produces folding and faulting of the sedimentary cover. Extensional tectonism trending roughly N-S has been taking place from the Middle Pleistocene to the Present; it is coeval with shoshonitic volcanic activity, and with sedimentation of fluvio-lacustrine terraces, torrential fans and moraines. Quaternary and active normal faults due to this tectonism, are located in a narrow zone more than 100 km-long between the High Plateaux and the Eastern Cordillera, and two 15 km-long fault sectors in the Eastern Cordillera. Characteristic Pleistocene scarps, 400 m or more high, are due to the cumulative normal offset, and there are also little scarps, with heights ranging between 2 and 20 m, which are related to Holocene fault reactivations. Recent fault reactivation on the Cuzco fault system, during the April 5, 1986 earthquake (m_b = 5.3), is due to the N-S trending extension. This state of stress, located at a mean elevation of roughly 3730 m, is generally homogeneous to different scales. The active Cuzco normal faults may be a consequence of adjustment between the compensated Western Cordillera and the undercompensated Eastern Cordillera, this latter being uplifted higher than its isostatic equilibrium due to compression acting on its eastern edge. The variation of the state of stress, during the Plio-Quaternary is in agreement with the variations of the compressional boundary forces. It may be explained by variation of the convergence rate or by the variation of pull-slab forces.     

Volcanic hazards in the surroundings of Pico de Orizaba,eastern Mexico

Volcanic hazards from Pico de Orizaba volcano are presented here tor the first time. Some 1.3 million people live within the hazard zone, which in the most severe case would encompass the Mexican Gulf coast, east of the volcano. Three major cities located in the eastern part of the hazard zone account for 800 000 of this population and about 200 000 people live within a 20 km radius of the volcano. Probability calculations are presented as an attempt to quantify the hazards in the surroundings of the volcano. Such quantification can be of use in planning for future land use within the hazard zones.A zone of about 10 km radius centred on the top crater is a high hazard zone for gravity-driven flows and fallout ejecta. For large volume eruptions, the radius could be extended to 120 km to the east and 60 km to the west. The asymmetrical distribution is related to the topography of the volcano. Hazards from Pyroclastic-fall deposits are principally to the west of the volcano, since easterly winds are dominant in the area lava-flow hazards are greatest within a 10 km radius from the summit crater. Pyroclastic flow hazards are high up to 20 km from the volcano summit.In the case of reactivation of the volcano, melting of a glacier covering the summit of Pico de Orizaba having a volume equivalent to some 45 × 10⁹ litres of water, would produce lahars which would descend the flanks of the volcano.