Raman spectroscopic studies of carbonates part I: High-pressure and high-temperature behaviour of calcite,magnesite, dolomite and aragonite

The room-temperature Raman spectra of aragonite, magnesite and dolomite have been recorded up to 30 GPa and 25 GPa, respectively and no phase changes were observed during compression, unlike calcite. The effect of temperature on the room-pressure Raman spectra of calcite, aragonite, magnesite and dolomite is reported up to 800–1100 K. The measured relative pressure and temperature-shifts of the Raman lines are greater for the lattice modes than for the internal modes of the CO₃ groups. These shifts are used to calculate the mode anharmonic parameters of the observed Raman modes; they are negative and their absolute values are smaller (close to 0) for the internal CO₃ modes than for the lattice modes (4–17 10^?5 K^?1). The temperature shifts of the lattice modes in calcite are considerably larger than those for dolomite and magnesite, and a marked non-linear increase in linewidth is observed above 400° C for calcite. This is consistent with an increasing relaxational component to the libration of the CO₃ groups about their threefold axes, premonitory to the rotational order-disorder transition at higher temperature. This behaviour is not observed for the other calcite structured minerals in this study. We examine systematic variations in the lattice mode frequencies and linewidths with composition, to begin to understand these differences in their anharmonic behaviour. Finally, we have used a simple Debye-Waller model to calculate atomic displacements in calcite, magnesite and dolomite with increasing temperature from the vibrational frequency data, to provide a direct comparison with atomic positional data from high-temperature structure refinements.     

Diffusion effects on oxygen isotope temperatures of slowly cooled igneous and metamorphic rocks

Recently obtained data on oxygen diffusion in feldspars, quartz, and hornblende permit the prediction of the apparent¹⁸O¹⁶O temperatures that would be measured in a rock that consisted only of those three minerals, and cooled slowly from high temperature. The computed temperatures would be based on the differences in the¹⁸O¹⁶O ratios between coexisting pairs of minerals. The present calculation takes into account the diffusion rates for oxygen as a function of temperature, the cooling rate of the rock, the mineral grain sizes, and the mode of the rock. For mineral grains 1 mm in radius, and a cooling rate of 10°C/m.y., the minimum difference in apparent temperature between quartz-feldspar and feldspar-hornblende pairs will be 115°C, despite the assumption of a normal, uneventful, slow cooling history to room temperature. Further, the apparent quartz-hornblende temperature will range over 30°C (590–620°C) depending on the mode of the rock. For a cooling rate of 1000°C/m.y., the apparent difference in temperature can be as much as 400°C. Consequently, consistency in temperatures obtained by oxygen isotope analysis should not be expected in most high-grade metamorphic rocks or igneous rocks which are cooled slowly. Departures from the pattern of temperatures obtained in this model would imply a very rapid quench from high temperature, or a complex history for the rock. For some minerals, including hornblende, the relation between temperature and the equilibrium fractionation of oxygen isotopes between coexisting phases has been derived from observed relations in natural specimens. The choice of the specimens used for such calibrations needs to be re-evaluated in light of these findings. This may result in a change in the equilibrium equation constants.An example from the literature, the San Jose tonalite, Baja California, Mexico, was modelled and yieldsδ¹⁸O concentrations in the minerals that correspond closely with the measured values. This suggests that the model used is appropriate, that the rock has had a simple thermal history, and that it cooled at 100–200°C/m.y. over the temperature range 800–500°C. The set of paleotemperatures obtained for a rock will, in general, yield neither the mineral closure temperatures nor the formation or crystallization temperatures. On the other hand, the cooling rate of the rock may be derived from the data. This, in turn, may have important tectonic implications with regard to denudation and uplift rates.     

Reconstructing fluvial bar surfaces from compound cross‐strata and the interpretation of bar accretion direction in large river deposits

The interpretation of fluvial styles from the rock record is based for a significant part on the identification of different types of fluvial bars, characterized by the geometric relationship between structures indicative of palaeocurrent and surfaces interpreted as indicative of bar form and bar accretion direction. These surfaces of bar accretion are the boundaries of flood‐related bar increment elements, which are typically less abundant in outcrops than what would be desirable, particularly in large river deposits in which each flood mobilizes large volumes of sediment, causing flood‐increment boundary surfaces to be widely spaced. Cross‐strata set boundaries, on the other hand, are abundant and indirectly reflect the process of unit bar accretion, inclined due to the combined effect of the unit bar surface inclination and the individual bedform climbing angle, in turn controlled by changes in flow structure caused by local bar‐scale morphology. This work presents a new method to deduce the geometry of unit bar surfaces from measured pairs of cross‐strata and cross‐strata set boundaries. The method can be used in the absence of abundant flood‐increment bounding surfaces; the study of real cases shows that, for both downstream and laterally accreting bars, the reconstructed planes are very similar to measured bar increment surfaces.     

An Observational Study of the Mesoscale Mistral Dynamics

We investigate the mesoscale dynamics of the mistral through the wind profiler observations of the MAP (autumn 1999) and ESCOMPTE (summer 2001) field campaigns. We show that the mistral wind field can dramatically change on a time scale less than 3 hours. Transitions from a deep to a shallow mistral are often observed at any season when the lower layers are stable. The variability, mainly attributed in summer to the mistral/land–sea breeze interactions on a 10-km scale, is highlighted by observations from the wind profiler network set up during ESCOMPTE. The interpretations of the dynamical mistral structure are performed through comparisons with existing basic theories. The linear theory of R. B. Smith [Advances in Geophysics, Vol. 31, 1989, Academic Press, 1–41] and the shallow water theory [Schär, C. and Smith, R. B.: 1993a, J. Atmos. Sci. 50, 1373–1400] give some complementary explanations for the deep-to-shallow transition especially for the MAP mistral event. The wave breaking process induces a low-level jet (LLJ) downstream of the Alps that degenerates into a mountain wake, which in turn provokes the cessation of the mistral downstream of the Alps. Both theories indicate that the flow splits around the Alps and results in a persistent LLJ at the exit of the Rhône valley. The LLJ is strengthened by the channelling effect of the Rhône valley that is more efficient for north-easterly than northerly upstream winds despite the north–south valley axis. Summer moderate and weak mistral episodes are influenced by land–sea breezes and convection over land that induce a very complex interaction that cannot be accurately described by the previous theories.     

Testing models of trace element geochemistry at Poços de Caldas

In order to test the geochemical models used in repository performance assessment, modelling groups were provided with selected major element analyses of Poços de Caldas groundwaters and asked to predict “blind” the solubility, speciation and limiting solid for a number of trace elements. This paper documents these predictions and compares them to field analyses. These tests illustrate particular stengths and weaknesses in current models/databases and allow recommendations for amendments/improvements to be made.     

Relation between seismic source parameters and mechanical properties of rocks: A case study

This study attempts to determine the relation between source parameters and mechanical properties of the rock matrix in which the microseismic events occur. For this purpose, accurate geological, mechanical and seismological data were acquired on a gas field experiencing induced seismicity due to its reservoir pressure drop. More than 30 deep boreholes (depth greater than 4 km) are concentrated in a 10×10×5 km volume, providing core samples for both geological and mechanical assessment. In this study, we focus on induced seismic events recorded by the local seismic network, over a three-year-long period. Characteristics of the seismic sources were obtained using spectral analysis and a dynamic model of failure. Results point out correlation between physical parameters of the seismic sources and the geomechanical properties of the rocks involved. Maximal static stress drops are found to be associated with the mechanical strength of the geological strata where the rupture occurs. The fracture size, using a circular model of failure, is also found to be dependent on the geomechanical setting. It is found that the size of the seismic fractures is dependent on the layer thickness and the prefracturation of the medium, both factors influencing the extension of preexisting discontinuities. The parameters of the seismic sources also show important changes when the gas reservoir is reached. The reservoir unit experienced a 45 MPa pore fluid pressure drop over a period of 20 years.     

Cookeite LiAl4(Si3Al)O10(OH)8: Experimental study and thermodynamical analysis of its compatibility relations in the Li2O−Al2O3−SiO2−H2O system

Three reactions limiting the stability field of the di-trioctahedral chlorite cookeite in the presence of quartz, in the system Li₂O−Al₂O₃−SiO₂−H₂O (LASH) have been reversed in the range 290–480°C, 0.8–14 kbar, using natural material close to the end member composition. Combining our results with known and estimated thermodynamic properties of the other minerals belonging to the LASH system, the enthalpy (-8512200 J/mol) and the entropy (504.8 J/mol^*K) of cookeite are calculated by a feasible solution space approach. The knowledge of these values allowed us to draw the first P−T phase diagram involving both the hydrated Li-aluminosilicates cookeite and bikitaite, which is applicable to a large variety of natural rock systems. The low thermal extent of the stability field of cookeite+quartz (260–480°C) makes cookeite a valuable indicator of low temperature conditions within a wide range of pressure (1–14 kbar).     

Single-crystal infrared reflectivity of pure Mg2SiO2 forsterite and (Mg0.86,Fe0.14)2SiO4 olivine

New polarized infrared reflectance spectra of pure synthetic forsterite and natural Fo₈₆-olivine have been recorded from 5000 to 100cm^-1. Out of the 35 expected infrared active modes, 33 have been observed (8 B_1u, 12 B_2u, 13 B_3u). The observed frequency shift from pure forsterite to Fo₈₆-olivine is consistent with the higher mass of the substituted iron. The substitution of only 14% of iron also reduces the overal far-infrared reflectivity of olivine as compared to pure forsterite. Several discrepancies associated with previous studies of forsterite are explained by our investigation. We suggest that some of the previous investigations were complicated by polarization mixing.