Jarmila Luptáková

Raman spectra of oriented and non-oriented Cu hydroxy-phosphate minerals: Libethenite, cornetite, pseudomalachite, reichenbachite and ludjibaite

Oriented cornetite [Cu3PO4(OH)3], libethenite [Cu2PO4(OH)] and pseudomalachite [Cu5(PO4)2(OH)4] and non-oriented reichenbachite [Cu5(PO4)2(OH)4] and ludjibaite [Cu5(PO4)2(OH)4] minerals from Ľubietová and Špania Dolina dump fields, Banská Bystrica, Slovakia were examined by polarized Raman spectroscopy. The examined minerals display the characteristic vibrational modes of PO4 and OH groups and further lattice modes. The PO4 stretching and bending vibrations of the investigated minerals occur between 1150 and 900 cm(-1) and between 700 and 350 cm(-1), respectively. On the other hand, the hydroxyl group stretching and bending modes appear above 3350 cm(-1) and between 900 and 700 cm(-1), respectively. The lattice vibrations occur below 350 cm(-1). The different bond distances of the PO4 groups readily explain the shift of the bands to higher or lower wavenumbers among the studied Cu hydroxy-phosphate minerals.

Oriented inclusions in apatite in a post-UHP fluid-mediated regime (Tromsø Nappe, Norway)

We report pyrrhotite, anhydrite and dolomite crystal rods in fluorapatite occurring in silicate-bearing carbonate rocks associated with UH P eclogites in the Tromso Nappe of the Scandinavian Caledonides in Norway. The apatite-rich rock (up to 10 vol. %) is composed of Mg-rich calcite-dolomite exsolutions, almandine-grossular garnet, low-jadeite clinopyroxene, magnesiohornblende, phlogopite, and accessory minerals represented mainly by zircon, Fe-Ti oxides and allanite. Fluorapatite occurring as euhedral crystals in the carbonate matrix and as inclusions in garnet and clinopyroxene shows up to 45 mol. % of the hydroxylapatite component, traces of CO 3 2− , probably CN − and small amounts of the britholite and ellestadite components. Pyrrhotite occurs as crystallographically oriented rods parallel to the c axis of the host hydroxyl-bearing fluorapatite either as a dense trellis or in the form of scarce inclusions. Precipitation of pyrrhotite in the fluorapatite was probably facilitated by a volatile sulphur phase ( e.g ., H 2 S), which was enclosed within the apatite nano-channels and interacted with Fe in apatite. Anhydrite and dolomite rods have also been identified in the apatite, pointing to the presence of HCO 3 − in the fluids. The anhydrite is also trapped by exsolved dolomite from calcite in the carbonate matrix. Crystallisation of anhydrite, and probably also the associated pyrrhotite, at about 550–650°C was deduced from calcite–dolomite thermometry. At these amphibolite-facies, post-UH P conditions rapid pyrrhotite precipitation in the host apatite is presumed. Relaxation of the fluorapatite structure in the a -axis direction during decompression facilitated the formation of the oriented inclusions in apatite.

High-pressure aragonite phenocrysts in carbonatite and carbonated syenite xenoliths within an alkali basalt

Abstract We describe the first observation of primary magmatic aragonite in carbonatite and carbonated syenite, occurring as xenoliths in a Pliocene basaltic diatreme located near the Hungary-Slovakia border. The aragonite-hosting matrix consists of disordered P-rich calcite, occasionally associated with trachyte glass. We interpret the aragonite growth as evidence of supra-lithostatic overpressure in the magmatic plumbing system that connected the crustal basaltic reservoir with the partial melting zone of the lithospheric mantle, and the disordered calcite ± trachyte as quenched residual, immiscible melts, generated close to the solidus of the carbonated alkali basalt differentiated in the crustal reservoir. The quenching event was a phreato-magmatic eruption within the stability field of the low-pressure calcite; this was triggered by advective overpressure, caused by expanding gas bubbles in a quasiincompressible silicate melt system. The high-pressure, pre-eruption origin of aragonite is indicated by enrichment in 13C compared to the associated calcite interpreted as a record of CO2 degassing at T > 500 °C. The oxygen (δ18O ranges of 22.1-24.5‰ V-SMOW in aragonite, 21.6-22.7‰ in calcite) and carbon (δ13C ranges of -4.4 to -5.9‰ V-PDB in aragonite, -11.9 to -12.7‰ in calcite) isotope signatures are consistent with a degassed carbonatite melt primarily derived from a subduction zone.

X-Ray Diffraction and Vibrational Spectroscopic Characteristics of Hydroxylclinohumite from Ruby-Bearing Marbles (Luc Yen District, Vietnam)

A honey-yellow hydroxylclinohumite from ruby-bearing marbles of the Luc Yen district in northern Vietnam was characterized by electron microprobe (EPMA), single-crystal X-ray diffraction (XRD), micro-Raman, and Fourier-transform infrared (FTIR) spectroscopy. The studied crystals correspond to nearly ideal clinohumite with the structural formula 4[Mg2SiO4][(Mg,Fe,Ti)(OH,F)2] and roughly equal F and OH proportions. Crystal structure analysis showed Ti substitution for Mg only at the Mg3 site. A Fourier-difference map revealed one hydrogen site associated with ninth oxygen atom. The calculated O–H bond distance was shorter than that in other natural clinohumites. FTIR revealed bands corresponding to combination of OH-stretching with Mg–OH and/or Fe–OH bending modes, combinations of OH− and Fe–OH vibrations, combination of fundamental bands of the Si–OH bonding, combination of OH− and Si–OH vibrations, and first (2) and the second (3) overtones of the OH-stretching vibration mode. Two groups of OH-stretching vibration and FTIR absorption bands at 3390–3420 cm−1 and 3560–3580 cm−1 show reversible temperature-dependent shift. The low-frequency bands absent in pure synthetic hydroxylclinohumites are assigned to OH-planar defects caused by Ti-for-Mg substitution.

Raman spectroscopic and microthermometric studies of authigenic quartz (the Pepper Mts., Central Poland) as an indicator of fluids circulation

Differently colored authigenic quartz crystals were found as the druses compound within mudstone heteroliths from the Pepper Mts. Shale Formation (Cambrian unit of the Holy Cross Mts., Central Poland). The genesis of this mineral was established on the basis of fluid inclusion study. Raman microspectroscopy was the key instrumental technique to identify the nature of the compounds trapped in the fluid inclusions. Methane (2917cm-1) or water vapor (broad band ~2500-3000cm-1) occur within two-phased primary inclusion assemblages, while nitrogen (2329cm-1) associated with methane and trace amount of carbon dioxide (1285, 1388cm-1) occur within secondary fluid inclusion assemblage. Temperatures of homogenization of primary fluid inclusions was obtained on the basis of heating experiments and ranged from 171° to 266°C. These values are much higher than expected for the diagenetic system without metamorphic changes what may imply hydrothermal origin of quartz crystals. The source of fluids is uncertain as in the Holy Cross Mts. there was no volcanic activity to the end of Late Devonian. However, fluids originated in metamorphic basin could use deep faults as the migration paths.

UHP metamorphism recorded by phengite eclogite from the Caledonides of northern Sweden : P-T path and tectonic implications

The Seve Nappe Complex (SNC) of the Scandinavian Caledonides records a well-documented history of high pressure (HP) and ultra-high pressure (UHP) metamorphism. Eclogites of the SNC occur in two ar ...