In Situ Raman Study of Liquid Water at High Pressure.

A pressure shift of Raman band of liquid water (H2O) may be an important tool for measuring residual pressures in mineral inclusions, in situ barometry in high-pressure cells, and as an indicator of pressure-induced structural transitions in H2O. However, there was no consensus as to how the broad and asymmetric water Raman band should be quantitatively described, which has led to fundamental inconsistencies between reported data. In order to overcome this issue, we measured Raman spectra of H2O in situ up to 1.2 GPa using a diamond anvil cell, and use them to test different approaches proposed for the description of the water Raman band. We found that the most physically meaningful description of water Raman band is the decomposition into a linear background and three Gaussian components, associated with differently H-bonded H2O molecules. Two of these components demonstrate a pronounced anomaly in pressure shift near 0.4 GPa, supporting ideas of structural transition in H2O at this pressure. The most convenient approach for pressure calibration is the use of "a linear background + one Gaussian" decomposition (the pressure can be measured using the formula P (GPa) = -0.0317(3)·ΔνG (cm-1), where ΔνG represents the difference between the position of water Raman band, fitted as a single Gaussian, in measured spectrum and spectrum at ambient pressure).

Incommensurately modulated twin structure of nyerereite Na1.64K0.36Ca(CO3)2.

The incommensurately modulated twin structure of nyerereite Na1.64K0.36Ca(CO3)2 has been first determined in the (3 + 1)-dimensional symmetry group Cmcm(α00)00s with modulation vector q = 0.383a*. Unit-cell values are a = 5.062 (1), b = 8.790 (1), c = 12.744 (1) Å. Three orthorhombic components are related by threefold rotation about [001]. Discontinuous crenel functions are used to describe the occupation modulation of Ca and some CO3 groups. The strong displacive modulation of the O atoms in vertexes of such CO3 groups is described using x-harmonics in crenel intervals. The Na, K atoms occupy mixed sites whose occupation modulation is described in two ways using either complementary harmonic functions or crenels. The nyerereite structure has been compared both with the commensurately modulated structure of K-free Na2Ca(CO3)2 and with the widely known incommensurately modulated structure of γ-Na2CO3.

Raman imaging of fluid inclusions in garnet from UHPM rocks (Kokchetav massif, Northern Kazakhstan).

Confocal Raman imaging of fluid inclusions in garnet porphyroblasts from diamond-grade metamorphic calc-silicate rocks from the Kumdy-Kol microdiamond deposit (Kokchetav Massif, Northern Kazakhstan) reveals that these fluid inclusions consist of almost pure water with different step-daughter phases (e.g., calcite, mica and rare quartz). These fluid inclusions are characterized by negative crystal shape of the host-garnet and they exclusively occur within the core of garnet porphyroblasts. These observations are consistent with their primary origin, most likely at ultrahigh-pressure (UHP) metamorphic conditions. The euhedral newly formed garnet, different in color and composition, was found to be associated with these fluid inclusions. It is proposed that newly formed garnet and water fluid inclusions appear by reaction between the hydrous fluid and the garnet-host. These fluid inclusions provide an unequivocal record of almost pure H(2)O fluids, indicating water-saturated conditions within subducted continental crust during prograde stage and/or ultrahigh-P metamorphism.

Brown diamonds from an eclogite xenolith from Udachnaya kimberlite, Yakutia, Russia.

We have performed petrographic and spectroscopic studies of brown diamonds from an eclogite xenolith from the Udachnaya pipe (Yakutia, Russia). Brown diamonds are randomly intermixed with colorless ones in the rock and often located at the grain boundaries of clinopyroxene and garnet. Brown diamonds can be characterized by a set of defects (H4, N2D and a line at 490.7 nm) which are absent in colorless diamonds. This set of defects is typical for plastically deformed diamonds and indicates that diamonds were likely annealed for a relatively short period after deformation had occurred. Excitation of brown colored zones with a 632.8 nm He-Ne laser produced the typical diamond band plus two additional bands at 1730 cm(-1) and 3350 cm(-1). These spectral features are not genuine Raman bands, and can be attributed to photoluminescence at ∼710 nm (1.75 eV) and ∼802 nm (1.54 eV). No Raman peak corresponding to graphite was observed in regions of brown coloration. Comparison with previous reports of brown diamonds from eclogites showed our eclogitic sample to have a typical structure without signs of apparent deformation. Two mechanisms with regard to diamond deformation are proposed: deformation of eclogite by external forces followed by subsequent recrystallization of silicates or, alternatively, deformation by local stress arising due to decompression and expansion of silicates during ascent of the xenolith to surface conditions.

First findings of monocrystalline aragonite inclusions in garnet from diamond-grade UHPM rocks (Kokchetav Massif, Northern Kazakhstan).

The presence of aragonite inclusions in garnet from diamond-grade metamorphic rocks from the Kokchetav Massif, Northern Kazakhstan was identified for the first time by means of Raman analyses and mapping. Aragonite appears within the inclusions up to 50 µm in size as a single crystal. These inclusions have rounded shape. The grain boundary between the host-garnet is smooth. No cracks occur around the aragonite inclusions. No significant shift in the main aragonite Raman band was measured. These observations indicate that residual pressure within the inclusion is minor. These findings imply either non-UHPM origin of the host garnet or significant plastic deformation of host minerals during retrograde stage. These features should be taken into account for recovery peak metamorphic conditions and modeling of exhumation processes of UHPM complexes.

Raman-based geobarometry of ultrahigh-pressure metamorphic rocks: applications, problems, and perspectives.

Raman-based geobarometry has recently become increasingly popular because it is an elegant way to obtain information on peak metamorphic conditions or the entire pressure-temperature-time (P-T-t) path of metamorphic rocks, especially those formed under ultrahigh-pressure (UHP) conditions. However, several problems need to be solved to get reliable estimates of metamorphic conditions. In this paper we present some examples of difficulties which can arise during the Raman spectroscopy study of solid inclusions from ultrahigh-pressure metamorphic rocks.

First finding of burkeite in melt inclusions in olivine from sheared lherzolite xenoliths.

For the first time burkeite was observed as a daughter phase in the melt inclusions in olivine by Raman spectroscopy. The olivine comes from sheared lherzolite xenoliths from the Udachnaya-East kimberlite pipe (Yakutia, Russia). This anhydrous sulfate-carbonate mineral (Na(6)(CO(3))(SO(4))(2)) is generally considered to be a characteristic mineral in saline soils or in continental lacustrine evaporite deposits. Recently, however, this mineral was identified in hydrothermal fluids. Our observations indicate that burkeite can also be formed from a mantle-derived melt.

Raman mapping of coesite inclusions in garnet from the Kokchetav Massif (Northern Kazakhstan).

Coesite inclusions occur in a wide range of lithologies and coesite is therefore a powerful ultrahigh-pressure (UHP) indicator. The transformation of coesite to quartz is evidenced by three optically well identifiable characteristics (e.g. palisade textures, radial crack patterns, polycrystalline quartz pseudomorphs). Under overpressure monomineralic coesite (on an optical basis), lacking the above transformation characteristics may survive. Raman micro-spectroscopy was applied on monomineralic coesite inclusions in garnet porphyroblasts from diamond-bearing garnet-clinozoisite-biotite gneisses of the Barchi-Kol area (Kokchetav Massif, Northern Kazakhstan). These coesite inclusions are euhedral and display a characteristic anisotropic hallo. However, Raman maps and separate spectra of these inclusions display shifted bands for coesite and quartz. Microscopically undetectable, quartz shows on the Raman map as a thin shell around coesite inclusion. Shift of the main coesite band allows to estimate their overpressure: coesite inclusions record 0-2.4 GPa in garnet and zircon. The quartz shell remains under lower pressure 0-1.6 GPa. The possible application of coesite and quartz Raman geobarometers for UHP metamorphic rocks is discussed.

Discrimination of metamorphic diamond populations by Raman spectroscopy (Kokchetav, Kazakhstan).

Metamorphic diamond is a powerful but frequently debated indicator for ultrahigh-pressure metamorphic (UHPM) conditions. Because of their small size, their optical identification needs confirmation. Characteristics of chemically extracted microdiamonds from Kokchetav, identified by different analytical methods, are used here for unambiguous in situ identification by Raman microspectroscopy. Differences appear in the diamond spectra and the Raman analytical method is explored as a helpful tool in the discrimination between diamond populations from four different UHPM lithologies of Kokchetav. Not considering the graphite-coated diamond, out of the reach of the laser wavelength used here, the comparison of these Kokchetav Raman spectra may provide additional information in other UHPM studies.