Thermal expansion and high-temperature P21/c–C2/c phase transition in clinopyroxene-type LiFeGe2O6 and comparison to NaFe(Si,Ge)2O6

A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) Å, β = 108.844(6)°, V = 442.75(16) ų, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the $(\bar{1}\,0\,1) A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) ?, β = 108.844(6)°, V = 442.75(16) ?³, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the ([`1] 0 1)(\bar{1}\,0\,1) plane, mostly along [0 1 0], and pure shear in the (0 1 0) plane due to the decrease of β. From comparison with silicate analogues, the germanate clinopyroxenes are more expansible, while the P2₁/c expands more than the C2/c phase. The evolution of Q ² (calculated as the normalized intensity of b-type reflections) with T in the framework of the Landau theory has been done using a standard expression for a first order phase transition. We observe a jump of Q ₀² = 0.538(2) at T _tr, with T _c of 481(7) K, b/a = −2,290 K, and c/a = 3,192 K, and thus far from being tri-critical point. A closely related composition (LiFe³⁺Si₂O₆) shows an equivalent phase transition at 228 K, which is very close to the tri-critical point and 561 K cooler. This result indicates that a change in the composition of tetrahedral sites can have dramatic effects on the P2₁/c ↔ C2/c displacive phase transition in clinopyroxenes. The major changes observed in the evolution of the crystal structure with T are observed in the M2 polyhedron, with a volume decrease by ca. 13.3%, compared to ca. 1.3% observed in the M1 polyhedron. The tetrahedra behave as rigid units with neither a significant change of volume at T > T _tr (<1‰), nor a change of tilting of the basal plane. No change in coordination is observed at T > T _tr in the M2 polyhedron, which remains sixfold coordinated although a strong deformation of this polyhedron is observed. This deformation is related to a strong change by 51.4° at T _tr of the kinking angle (O3–O3–O3 angle) of the B-chain of tetrahedra, which switches from O-rotated to S-rotated [from 143.3(5)° to 194.7(6)°]. The A-chain is S-rotated at T < T _tr [206.8(5)° at 703 K] and extends by 12° at the transition.     

Opening of the Fram Strait gateway: A review of plate tectonic constraints

We have revised the regional crustal structure, oceanic age distribution, and conjugate margin segmentation in and around the Lena Trough, the oceanic part of the Fram Strait between the Norwegian–Greenland Sea and the Eurasia Basin (Arctic Ocean). The Lena Trough started to open after Eurasia–Greenland relative plate motions changed from right-lateral shear to oblique divergence at Chron 13 times (33.3 Ma; earliest Oligocene). A new Bouguer gravity map, supported by existing seismic data and aeromagnetic profiles, has been applied to interpret the continent–ocean transition and the influence of Eocene shear structures on the timing of breakup and initial seafloor spreading. Assuming that the onset of deep-water exchange depended on the formation of a narrow, oceanic corridor, the gateway formed during early Miocene times (20–15 Ma). However, if the initial Lena Trough was blocked by terrigenous sediments or was insufficiently subsided to allow for deep-water circulation, the gateway probably formed with the first well developed magnetic seafloor spreading anomaly around Chron 5 times (9.8 Ma; Late Miocene). Paleoceanographic changes at ODP Site 909 (northern Hovgård Ridge) are consistent with both hypotheses of gateway formation. We cannot rule out that a minor gateway formed across stretched continental crust prior to the onset of seafloor spreading in the Lena Trough. The gravity, seismic and magnetic observations question the prevailing hypotheses on the Yermak Plateau and the Morris Jesup Rise as Eocene oceanic plateaus and the Hovgård Ridge as a microcontinent.     

Occurrence and use of mineral and thermal waters in Poland

Mineral and thermal waters are defined according to Polish geological and mining law. Their occurrence in particular hydrogeological provinces of the country is characterized. Besides their use in balneotherapeutics, their role as a heat carrier and source of chemical raw materials is stressed. Topics mentioned requiring further research are: the origin of saline formation waters and the origin of CO₂ in carbonated waters.     

5-alkylsalicylaldoximes as collectors in flotation of sphalerite,smithsonite and dolomite in a Hallimond tube

Flotation tests for sphalerite, smithsonite and dolomite were carried out in a Hallimond tube at various pH values and two concentrations of collector.Adsorption of 5-alkylsalicylaldoximes on the surface of minerals was examined and isotherms for 5-butylsalicylaldoxime plotted.It was shown that sorption intensity of 5-alkylsalicylaldoximes on the surface of minerals decreased in the order: smithsonite, sphalerite and dolomite.Relationship between length of aliphatic chain and collecting activity of 5-alkylsalicylaldoximes was investigated in microflotation tests in a Hallimond tube.5-Propylsalicylaldoxime proved to have the best selectivity in flotation for the range of parameters studied, taking the difference in flotation rates of smithsonite and dolomite as a criterion.It was found that modifications of pH value resulted in changes in both adsorption and flotation.     

UHP metamorphism recorded by kyanite-bearing eclogite in the Seve Nappe Complex of northern Jämtland,Swedish Caledonides

The first evidence for ultrahigh-pressure (UHP) metamorphism in the Seve Nappe Complex of the Scandinavian Caledonides is recorded by kyanite-bearing eclogite, found in a basic dyke within a garnet peridotite body exposed close to the lake Friningen in northern Jämtland (central Sweden). UHP metamorphic conditions of ~ 3 GPa and 800 °C, within the stability field of coesite, are constrained from geothermobarometry and calculated phase equilibria for the peak-pressure assemblage garnet + omphacite + kyanite + phengite. A prograde metamorphic evolution from a lower P–T (1.5–1.7 GPa and 700–750 °C) stage during subduction is inferred from inclusions of pargasitic amphibole, zoisite and kyanite in garnet cores. The post-UHP evolution is constrained from breakdown textures, such as exsolutions of kyanite and silica from the Ca-Eskola clinopyroxene. Near isothermal decompression of eclogite to lower crustal levels (~ 0.8–1.0 GPa ) led to formation of sapphirine, spinel, orthopyroxene and diopside at granulite facies conditions. Published age data suggest a Late Ordovician (460–445 Ma) age of the UHP metamorphism, interpreted to be related to subduction of Baltoscandian continental margin underneath an outboard terrane, possibly outermost Laurentia, during the final stages of closure of the Iapetus Ocean. The UHP rocks were emplaced from the hinterland collision zone during Scandian thrusting of the nappes onto the Baltoscandian foreland basin and platform. The record of P–T conditions and geochonological data from UHP rocks occurring within the allochthonous units of the Scandinavian Caledonides indicate that Ordovician UHP events may have affected much wider parts of the orogen than previously thought, involving deep subduction of the continental crust prior to final Scandian collision between Baltica and Laurentia.     

Chemical and structural relations of epitaxial xenotime and zircon substratum in sedimentary and hydrothermal environments: a TEM study

Xenotime overgrowths on detrital zircon in siliciclastic sediments have been reported in numerous studies. However, in natural samples, solid solution of zircon and xenotime is limited to near-end-member compositions. In order to characterize the interface region between both minerals and to draw inferences on the growth mechanisms of authigenic xenotime, we studied xenotime overgrowths on detrital zircon grains from two Phanerozoic sandstone samples with contrasting post-depositional histories. In one sample, the small (≤10 μm), pyramidal xenotime overgrowths are of diagenetic origin and grew without major discontinuity on the detrital zircon grain. The second sample shows up to >50-μm-wide, porous and inclusion-rich, hydrothermal xenotime overgrowths on detrital zircon, whereas the transition zone between both minerals is accompanied by large pore volume. Chemical compositions of the xenotime precipitates from the two samples differ particularly in Y, REE, Th and Sc concentrations, whereas high MREE availability in the diagenetic sample and the presence of Sc in the hydrothermal sample, respectively, appear to have promoted xenotime growth. Transmission electron microscopy on electron-transparent foils cut from the interface region shows that both the diagenetic xenotime and the hydrothermal xenotime are crystalline and grew in optical and crystallographic continuity to their detrital zircon substrata. Only a narrow transition zone (≤90 nm—diagenetic sample, 200–300 nm—hydrothermal sample) between zircon and xenotime is in part made up of nanometre-scale crystalline domains that are slightly distorted and may have formed from dissolution–re-precipitation processes at the zircon rim along with precipitation from the respective fluid.