HTP21/c–C2/c phase transition and kinetics of Fe2+–Mg order–disorder of an Fe-poor pigeonite: implications for the cooling history of ureilites

A natural Ca-poor pigeonite (Wo₆En₇₆Fs₁₈) from the ureilite meteorite sample PCA82506-3, free of exsolved augite, was studied by in situ high-temperature single-crystal X-ray diffraction. The sample, monoclinic P2₁/c, was annealed up to 1,093°C to induce a phase transition from P2₁/c to C2/c symmetry. The variation with increasing temperature of the lattice parameters and of the intensity of the b-type reflections (h + k = 2n + 1, present only in the P2₁/c phase) showed a displacive phase transition P2₁/c to C2/c at a transition temperature T _Tr = 944°C, first order in character. The Fe–Mg exchange kinetics was studied by ex situ single-crystal X-ray diffraction in a range of temperatures between the closure temperature of the Fe–Mg exchange reaction and the transition temperature. Isothermal disordering annealing experiments, using the IW buffer, were performed on three crystals at 790, 840 and 865°C. Linear regression of ln k _D versus 1/T yielded the following equation: ln k_\textD = - 3717( ±416)/T(K) + 1.290( ±0.378);    (R² = 0.988) \ln \,k_{\text{D}} = - 3717( \pm 416)/T(K) + 1.290( \pm 0.378);\quad (R^{2} = 0.988) . The closure temperature (T _c) calculated using this equation was ∼740(±30)°C. Analysis of the kinetic data carried out taking into account the e.s.d.'s of the atomic fractions used to define the Fe–Mg degree of order, performed according to Mueller’s model, allowed us to retrieve the disordering rate constants C ₀ K _dis⁺ for all three temperatures yielding the following Arrhenius relation: ln( C₀ K_\textdis ⁺ ) = ln K₀ - Q/(RT) = 20.99( ±3.74) - 26406( ±4165)/T(K);    (R² = 0.988) \ln \left( {C_{0} K_{\text{dis}}^{ + } } \right) = \ln \,K_{0} - Q/(RT) = 20.99( \pm 3.74) - 26406( \pm 4165)/T(K);\quad (R^{2} = 0.988) . An activation energy of 52.5(±4) kcal/mol for the Fe–Mg exchange process was obtained. The above relation was used to calculate the following Arrhenius relation modified as a function of X _Fe (in the range of X _Fe = 0.20–0.50): ln( C₀ K_\textdis ⁺ ) = (21.185 - 1.47X_\textFe ) - \frac(27267 - 4170X_\textFe )T(K) \ln \left( {C_{0} K_{\text{dis}}^{ + } } \right) = (21.185 - 1.47X_{\text{Fe}} ) - {\frac{{(27267 - 4170X_{\text{Fe}} )}}{T(K)}} . The cooling time constant, η = 6 × 10⁻¹ K⁻¹ year⁻¹ calculated on the PCA82506-3 sample, provided a cooling rate of the order of 1°C/min consistent with the extremely fast late cooling history of the ureilite parent body after impact excavation.     

The Calabrian Stage redefined

The name Calabrian was introduced in the geological literature by the French stratigrapher Maurice Gignoux in 1910, and later described in his important monograph （633 pages） ＂Les formations marines pliocknes et quaternaires de l＇ltalie du sud et de la Sicile ＂published in 1913. Detailed data were provided on several sections （Santa Maria di Catanzaro, Caraffa, Monasterace, Palermo） and on their fossil content. The Calabrian Stage has commonly been used for over fifty years as the oldest subdivision of the Qua- ternary, notably in the time scales of Berggren ＆ van Cou- vering （1974） and Haq ＆ Eysinga （1987）. However, after the GSSP for the Pliocene/Pleistocene boundary （P/P） was approved by INQUA in 1982 and ratified by lUGS in 1984 at the Vrica section of Calabria, there was a decline in the usage of the stage name, and an increasing tendency by many Quaternary workers to question the boundary stratotype. This was because there was increasing evidence that it did not correspond to the beginning of the ＂ice age＂. In doing so, they were not complying with the recommendations presented at the 18th International Geological Congress （IGC） in London, 1948 （Oakley, 1950）.     

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.     

The Density and Masses of Obscured Black Holes

Recent Chandra and XMM-Newton surveys have uncovered a large fraction of the obscured AGN responsible of the hard X-ray background. One of the most intriguing results of extensive programs of follow-up observations concerns the optical and near-infrared properties of the hard X-ray sources counterparts. More specifically, for a significant fraction of hard X-ray obscured sources the AGN responsible of the high X-ray luminosity remains elusive over a wide range of wavelengths from soft X-rays to near-infrared. This very observational result opens the possibility to investigate the host of bright obscured quasars in some detail. Here we briefly report on some preliminar results obtained for a small sample of elusive AGN in the HELLAS2XMM survey.     

An ESA NEOCC Effort to Eliminate High Palermo Scale Virtual Impactors

In this work we summarize the initial results of a targeted effort of the ESA NEO Coordination Centre to obtain additional observational data in order to eliminate or reduce the impact probability estimate of a subset of the known near-Earth objects representing the highest fraction of the total known impact risk, as measured by the Palermo Scale.     

δ 11B as tracer of slab dehydration and mantle evolution in Western Anatolia Cenozoic Magmatism

Boron isotope data are presented for Cenozoic Western Anatolia rocks, which define two main associations: (i) calc-alkaline, shoshonitic and ultra-potassic rocks (Early to Middle Miocene); and (ii) Late Miocene–Quaternary intraplate alkali basalts. Boron data, together with Sr–Nd isotope and other trace elements, are consistent with a progressive dehydration of the slab, producing fluid phases gradually depleted in B (and ¹¹B). These fluids were added to the supraslab mantle, triggering a partial melting that gave rise to orogenic magmatism. The stretching and tearing of the slab caused by the faster convergence of Greece over Africa with respect to Anatolia facilitated an interaction of the upwelling subslab asthenosphere with residual slab-fluids during the Late Miocene followed by production of typical intraplate magmas during the Pleistocene–Holocene, whose relatively high δ¹¹B (approximately −2‰) is considered representative of the local asthenosphere not affected by subduction contamination.     

Detection and extraction of signals from the epoch of reionization using higher-order one-point statistics

Detecting redshifted 21-cm emission from neutral hydrogen in the early Universe promises to give direct constraints on the epoch of reionization (EoR). It will, though, be very challenging to extract the cosmological signal (CS) from foregrounds and noise which are orders of magnitude larger. Fortunately, the signal has some characteristics which differentiate it from the foregrounds and noise, and we suggest that using the correct statistics may tease out signatures of reionization. We generate mock data cubes simulating the output of the Low Frequency Array (LOFAR) EoR experiment. These cubes combine realistic models for Galactic and extragalactic foregrounds and the noise with three different simulations of the CS. We fit out the foregrounds, which are smooth in the frequency direction, to produce residual images in each frequency band. We denoise these images and study the skewness of the one-point distribution in the images as a function of frequency. We find that, under sufficiently optimistic assumptions, we can recover the main features of the redshift evolution of the skewness in the 21-cm signal. We argue that some of these features – such as a dip at the onset of reionization, followed by a rise towards its later stages – may be generic, and give us a promising route to a statistical detection of reionization.