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.     

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.     

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.     

Packing states of ideal reservoir sands: Insights from simulation of porosity reduction by grain rearrangement

The question being tackled in this study is to which extent grain rearrangement contributes to porosity reduction in very well sorted quartzose sands (ideal reservoir sands). A numerical model, RAMPAGE (an acronym of random packing generator), has been developed to address this long-standing problem. RAMPAGE represents a synthesis of various algorithms designed to simulate packing of equal-sized spheres, which have been used to represent ideal solids, liquids, and gases, as well as natural porous media. The results of RAMPAGE simulations compare favourably to theoretical and experimental data from various disciplines and allow delineation of the field of gravitationally stable random packing of equal-sized spheres in the 2-D state space of porosity (P) versus mean coordination number (N). Three end-member packing states have been identified: random loose packing (RLP: P = 45.4%, N = 5.2), random close packing (RCP: P = 36.3%, N = 7.0), and bridged random close packing (Bridged RCP: P = 39.5%, N = 5.2). Unlike previously proposed models, RAMPAGE can simulate the transition from RLP to any other point in the stability field. The RLP state is fully consistent with wet-packed porosities of synthetic sands with lognormal mass-size distributions reported in the literature. The much higher in-situ porosity values reported for modern (air-packed) sands are unlikely to be preserved at depth on geological time scales. Data on the relation between intergranular volume and burial depth indicate that the observed intergranular volume reduction in the upper ~ 800 m of the sediment column corresponds to the evolution of RLP to RCP, and is thus fully explained by non-destructive grain rearrangement.     

Rock displacement and thermal expansion study at historic heritage sites in Slovakia

The paper discusses the results of the research devoted to the preservation of cultural heritage carried out within last two decades in Slovakia. The aim of the study depended on monitoring of selected castle rocks showing instability problems due to extremely slow displacements of creep character. Apart from traditional methods of investigation at one test site (Spis Castle), authors implemented in their work the study of thermal expansion of the rocks as a result of seasonal periodic temperature changes having potential influence on displacements and numerical modeling in order to understand better the landslide failure mechanism. The results obtained from all study sites confirmed that even slow movements have to be implemented into preservation and stabilization works in order to safeguard the sites of great historic value.