Excess heat capacity and entropy of mixing along the chlorapatite–fluorapatite binary join

The heat capacity at constant pressure, C _p, of chlorapatite [Ca₅(PO₄)₃Cl – ClAp], and fluorapatite [Ca₅(PO₄)₃F – FAp], as well as of 12 compositions along the chlorapatite–fluorapatite join have been measured using relaxation calorimetry [heat capacity option of the physical properties measurement system (PPMS)] and differential scanning calorimetry (DSC) in the temperature range 5–764 K. The chlor-fluorapatites were synthesized at 1,375–1,220°C from Ca₃(PO₄)₂ using the CaF₂–CaCl₂ flux method. Most of the chlor-fluorapatite compositions could be measured directly as single crystals using the PPMS such that they were attached to the sample platform of the calorimeter by a crystal face. However, the crystals were too small for the crystal face to be polished. In such cases, where the sample coupling was not optimal, an empirical procedure was developed to smoothly connect the PPMS to the DSC heat capacities around ambient T. The heat capacity of the end-members above 298 K can be represented by the polynomials: C _p^ClAp = 613.21 − 2,313.90T ^−0.5 − 1.87964 × 10⁷ T ⁻² + 2.79925 × 10⁹ T ⁻³ and C _p^FAp = 681.24 − 4,621.73 × T ^−0.5 − 6.38134 × 10⁶ T ⁻² + 7.38088 × 10⁸ T ⁻³ (units, J mol⁻¹ K⁻¹). Their standard third-law entropy, derived from the low-temperature heat capacity measurements, is S° = 400.6 ± 1.6 J mol⁻¹ K⁻¹ for chlorapatite and S° = 383.2 ± 1.5 J mol⁻¹ K⁻¹ for fluorapatite. Positive excess heat capacities of mixing, ΔC _p^ex, occur in the chlorapatite–fluorapatite solid solution around 80 K (and to a lesser degree at 200 K) and are asymmetrically distributed over the join reaching a maximum of 1.3 ± 0.3 J mol⁻¹ K⁻¹ for F-rich compositions. They are significant at these conditions exceeding the 2σ-uncertainty of the data. The excess entropy of mixing, ΔS ^ex, at 298 K reaches positive values of 3–4 J mol⁻¹ K⁻¹ in the F-rich portion of the binary, is, however, not significantly different from zero across the join within its 2σ-uncertainty.     

UAV-based spatiotemporal thermal patterns of permafrost slopes along the Qinghai–Tibet Engineering Corridor

Thermal infrared remote sensing technology based on unmanned aerial vehicle (UAV) was applied to estimate the spatial distribution of ground surface temperatures on permafrost slopes and evaluate the thermal influence of nearby engineering infrastructure. This paper presents a method that uses a miniature UAV with a thermal infrared sensor to collect thermal images with high temporal–spatial resolution. Moreover, spatial analysis is used to effectively evaluate the relationship between engineering infrastructure and permafrost slopes in the Qinghai–Tibet Engineering Corridor (QTEC), China. To test the method, aerial measurements were collected from 11:00 to 17:00 in July and August of 2017 at two permafrost slopes along the QTEC, where the Qinghai–Tibet Highway (QTH), Qinghai–Tibet Railway (QTR), and electric towers were built on permafrost slopes. The differences of ground surface temperature between the highway and the surrounding soil were largest at 11:00 and 17:00; the differences were smaller at noon to approximately 15:00 when the difference was minimal, and the differences began to increase after 15:00. The distances of the thermal influence of the highway, railway, and electric towers on the surrounding permafrost slopes are approximately 12–14, 8–10, and 2–4 m, respectively. The results indicate that the degree of influence of engineering structures on permafrost slopes is as follows: QTH?>?QTR?>?electric towers. This study is the first to use UAV-based thermal infrared remote sensing to evaluate the thermal dynamics of permafrost slopes along the QTEC. These results may provide new insights into the future design, construction, and maintenance of engineering structures on permafrost slopes.     

High-pressure behaviour along the jadeite NaAlSi2O6–aegirine NaFeSi2O6 solid solution up to 10 GPa

The volume variation as a function of pressure along the jadeite–aegirine solid solution was determined at room temperature up to pressures between 6.5 and 9.7 GPa by single-crystal X-ray diffraction. The unit-cell volumes collected at room pressure for the different compositions indicate a slight deviation from linearity along the join. The pressure–volume data have been fitted using a third-order Birch-Murnaghan equation of state (BM3-EoS). The bulk modulus, K _T0, varies from 134.0(7) GPa for pure jadeite to 116.1(5) GPa for pure aegirine. Its evolution with composition along the join is not linear and can be described by the following second order polynomial:

A Mössbauer and FTIR study of synthetic amphiboles along the magnesioriebeckite – ferri-clinoholmquistite join

A series of amphiboles along the magnesioriebeckite—Na₂Mg₃Fe³⁺ ₂Si₈O₂₂(OH)₂– ferri-clinoholmquistite—Li₂Mg₃Fe³⁺ ₂Si₈O₂₂(OH)2 - join, defined by the ^BLi^B Na_–1 exchange vector, were hydrothermally synthesized at 700°C, 0.4 GPa, NNO + 1 redox conditions. Powder XRD and SEM-EDAX showed a very high (> 90%) amphibole yield for all samples. X-ray patterns were indexed in the C2/m space group; refined cell-parameters show a linear decrease of a and as a function of chemistry. IR spectra in the OH-stretching region show four main and rather sharp bands; these are assigned to Mg and Fe²⁺ at M(1,3), and indicate that the obtained amphiboles depart from the nominal octahedral composition (^M1,3Mg₃). The IR spectra also show that there is an increasing filling-up of the A-site for increasing Na in the system (increasing solid-solution toward, arfvedsonite). Mössbauer spectra show four well-defined quadrupole doublets which are assigned to Fe³⁺ at M2 and to Fe²⁺ at M1, M3 and M4, respectively. The Fe³⁺/Fe²⁺ content derived from fitted peak areas show variable Fe³⁺ concentration along the series. Mössbauer spectra also show a distinct alteration of ⁵⁷Fe hyperfine parameters with changing Na–Li at M4. The most evident variation is observed for the quadrupole splitting of Fe³⁺ at M2, which increases by 50% from ferri-clinoholmquistite to magnesio-riebeckite; this suggest that the M2 octahedron in ferri-clinoholmquistite is much closer to the ideal geometry than the M2 octahedron in magnesio-riebeckite. Mössbauer spectra show also a well-defined increase in the Fe²⁺ quadrupole splitting of the M1 and M3 octahedra, which is attributed to the Na–Li distribution at the B-sites.     

Peierls–Nabarro modelling of dislocations in diopside

The core structures of dislocations in diopside have been calculated within the Peierls model, which assumes a planar core. 1/2<110> dislocations can dissociate into two collinear partial dislocations. We show that [001] glide is very difficult in (010) and that a non-collinear dissociation of [001](100) (modelled within a Peierls–Nabarro–Galerkin approach) makes glide equally easy in (100) and {110}. A widely spread core structure corresponding to a low lattice friction has been found for [100](010) and [010](100) dislocations which is not supported by mechanical data and, together with TEM observations, suggests that another, probably non-planar core structure is possible for these dislocations.     

Long-term thermal stability study of the typical embankment along the Qinghai-Tibet Railway in warm permafrost regions北大核心CSCD

Using the long-term ground temperature monitoring data of the permafrost zone along the Qinghai-Tibet Railway from 2006 to 2020,three types of typical roadbed structures were analyzed. Traditional embankment（TE）,U-shaped crushed rock embankment（UCRE）and crushed rock revetment embankment（CRRE）were included the three types of typical roadbed,which were selected to the long-term monitoring sections within the warm permafrost zones. The evolution of ground temperature field,mean annual ground temperature （MAGT）and annual maximum ground temperature（AMGT）in the depth range of 20 m under the embankment were analyzed and studied since 15 years of operation. The monitoring and analysis results show that：the growth rate of MAGT under the left and right shoulders of the TE is always higher than that of the same depth in the natural site. The MAGT under the UCRE is always lower than the natural site and always maintains a certain difference,whereas,the difference in ground temperature under the left and right shoulders is also not negligible. The MAGT of the left shoulder in the CRRE is not much different from that of the natural hole,while the MAGT of the right shoulder is always lower than that of the natural hole,and the differ in ground temperature between the left and right shoulders is smaller than that of the UCRE. The artificial permafrost table（APT）under the TE is always lower than that of in the natural site. Both the UCRE and CRRE,the APT in the left and right shoulders of them has been elevated into the embankment,and the differ of APT between the left and right shoulders is about 1. 0~1. 5 m. the differ of APT between the left and right shoulders in the CRRE is slightly lower than that of UCRE. Overall,because of the influence of thermal disturbance about engineering and climate warming,the TE in the warm permafrost zones cannot keep the thermal stability of permafrost under the embankment. Some active-cooling and reinforcement measures need to be taken. Both of the UCRE and CRRE,have a certain active-cooling effect on the permafrost under embankment,but the differ in ground temperature between the left and right shoulders still needs to be taken seriously. © 2022 Science Press (China).     

Did the circum-Rodinia subduction trigger the Neoproterozoic rifting along the Congo–Kalahari Craton margin?

International Journal of Earth Sciences - Early Neoproterozoic metaigneous rocks occur in the central part of the Kaoko–Dom Feliciano–Gariep orogenic system along the coasts of the...     

Experimental Na-K distribution between amphiboles and aqueous chloride solutions, and a mixing model along the richterite – K-richterite join

The cation exchange equilibrium has been investigated by hydrothermal experiments at 700 and 800°C at 200 MPa. To avoid equilibration problems of conventional exchange experiments, we synthesized amphiboles with an excess fluid allowing exchange between solid and fluid during the experiment. The exchangeable cations Na and K were provided as excess 1 to 2n chloridic solution. These exchange syntheses can be described by the reaction equation with ^(aq) for hydroxides and chlorides in aqueous solutions and _{( s )} and _{( p )}?=?start and product fluid. The amphiboles grew in presence of the exchange fluid and adjusted their stoichiometry in equilibrium with the fluid phase. The solid products consist of more than 99% amphibole (Na,K-richterite_ss) with traces of diopside and quartz. The amphiboles are up to 1?mm long and often ≈ 40 μm thick. Detailed EMP- and HRTEM-observations show that they are chemically homogeneous and structurally wellordered. The experimental results give consistent phase relations in the reciprocal ternary system Na-richterite–K-richterite–NaCl–KCl. We analysed the product fluid with AAS- and ICP-methods. The Na-K distribution coefficients between fluid and amphiboles of the richterite–K-richterite join are close to unity at 700°C and 800°C at 200 MPa. Small systematic deviations are explained by a symmetric solution model for the A-position of the amphiboles. Using ideal mixing for H₂O-NaCl-KCl fluids, a mixing model for the system richterite–K-richterite is presented. We suggest that the composition of richterite solid solutions can be used as a sensor for NaCl/KCl-ratios in metamorphic fluids.     

The Thermal Volume Changes of the Callovo–Oxfordian Claystone

There are very few data on the thermoplastic behaviour of claystones, while their knowledge is necessary in understanding long-term behaviour of high-level radioactive waste confining systems. In this paper, a number of thermomechanical parameters of the Callovo–Oxfordian claystone, the possible host rock of radioactive waste in France, are presented. These parameters were obtained from experiments performed on a hollow cylinder cell. The short drainage path of this device allows a good saturation in a reasonably short time; also, the good drainage conditions and reasonable homogeneity of pore pressure during the tests in such a low-permeability material. The saturation procedure was performed under in-site stresses prior to testing to reduce the swelling effect during hydration. The thermomechanical experimental programme conducted here evidenced a plastic contraction of the claystone during drained heating under in-situ stress conditions, like in normally consolidated soils. Previous loading induced a dilating–contracting response comparable to that of overconsolidated clays. Finally, whereas the elastic response appeared to be temperature independent, the plastic compressibility investigated through a drained isothermal isotropic compression test at 80 °C increased compared to that at 25 °C. These first results should be confirmed by further thermomechanical investigation on claystones.     

Octahedral-site Fe2+ quadrupole splitting distributions from Mössbauer spectroscopy along the (OH, F)-annite join

We have performed a detailed Mössbauer study of synthetic annites on the (OH, F)-join. Recently developed data treatment and spectral analysis methods were used to extract true intrinsic Fe²⁺ quadrupole splitting distributions (QSDs) that represent the most information that can be resolved from the spectra. The overall room temperature (RT) QSDs can be consistently interpreted in terms of four QSD contributions (or populations) centered at: QS_HH2.55 mm/s for Fe²⁺O₄(OH)₂ octahedra (cis and trans not resolved), QS_HF 2.35 mm/s for Fe²⁺O₄(OH)F octahedra (cis and trans not resolved), QS_cFF2.15 mm/s for cis-Fe²⁺O₄F₂ octahedra, and QS_tFF 1.5 mm/s for trans-Fe²⁺O₄F₂ octahedra. Each such contribution has a width ( 0.2 mm/s) caused by distortions of the octahedra. Minor contributions due to Fe²⁺O₅(OH) and Fe²⁺O₅F octahedra probably also contribute to the overall Fe²⁺ QSDs. The ferric iron spectral components were also characterized. Here, two distinct types of octahedral Fe³⁺ contributions are seen and interpreted as being due mainly to Fe³⁺O₅OH and Fe³⁺O₅F octahedra, respectively. Tetrahedral Fe³⁺ is seen only in the OH-annite end-member and the total Fe³⁺ content drops significantly on addition of F. On leave from: Department of Materials Physics, University of Science and Technology Beijing, 100083 Beijing, China     

Petrogenetic variability along the North–South Propagating Spreading Center of the North Fiji Basin

Summary Previous studies on propagating rifts suggested that segmentation of a spreading axis could represent the superficial mark of mantle behavior (Sinton et al., 1983; Nicolas, 1989; Gente et al., 1995). The study of North–South Propagating Spreading Center (NS-PSC) from the North Fiji Basin (NFB) brings new insights to this debate. Basalts from the central part of the propagator have more variable incompatible and isotopic ratios then those from its northern tip. A model of dynamic partial melting of a thermally and slightly geochemically and isotopically heterogeneous mantle is proposed. Beneath the central segment, the partial fusion starts deeper (ca. 30km) and reaches a higher rate (ca. 22%). Further open system differentiation occurs within shallow permanent magma reservoirs along most of the central segment. Below the segment closest to the tip of the propagator the partial fusion starts shallower (ca. 25km) and stays at a lower rate (ca. 16%). The maximum of differentiation occurs close to the propagator, in small, periodically disconnected, magma bodies resulting in the production of ferrobasalts close to the tip. In order to explain these variations, the presence of an asthenospheric diapir focused beneath the central part of the NS-PSC is proposed. The petrogenetic processes of propagating spreading centers of mature oceanic basins or back-arc basins are identical.     

Neutron diffraction determination of the cell dimensions and thermal expansion of the fluoroperovskite KMgF3 from 293 to 3.6 K

The cell dimensions of the fluoroperovskite KMgF₃ synthesized by solid state methods have been determined by powder neutron diffraction and Rietveld refinement over the temperature range 293–3.6 K using Pt metal as an internal standard for calibration of the neutron wavelength. These data demonstrate conclusively that cubic $ Pm\overline{3} m The cell dimensions of the fluoroperovskite KMgF₃ synthesized by solid state methods have been determined by powder neutron diffraction and Rietveld refinement over the temperature range 293–3.6 K using Pt metal as an internal standard for calibration of the neutron wavelength. These data demonstrate conclusively that cubic KMgF₃ does not undergo any phase transitions to structures of lower symmetry with decreasing temperature. Cell dimensions range from 3.9924(2) ? at 293 K to 3.9800(2) ? at 3.6 K, and are essentially constant within experimental error from 50 to 3.6 K. The thermal expansion data are described using a fourth order polynomial function.     

Eocene Basins on the SE Tibetan Plateau: Markers of Minor Offset along the Xuelongshan–Diancangshan–Ailaoshan Structural System

The offset of geological bodies provides robust evidence of displacement along a fault or ductile shear zone. The amount of displacement along the Xuelongshan–Diancangshan–Ailaoshan structural system, southeastern Tibetan Plateau, is uncertain because of the lack of offset geological markers. This NNW–SSE-trending system is developed in three isolated metamorphic complexes and interjacent nonmetamorphosed rocks. They are expected to record similar post-Eocene strain, although their structural pa...     

Submicron-sized fluid inclusions and distribution of hydrous components in jadeite,quartz and symplectite-forming minerals from UHP jadeite–quartzite in the Dabie Mountains,China: TEM and FTIR investigation

Fluid inclusions and clusters of water molecules at nanometer-to submicron-scale in size have been investigated using transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR) in jadeite, quartz and symplectite aegirine–augite, albite, taramite and magnetite corona minerals from ultrahigh-pressure (UHP) jadeite–quartzite at Shuanghe, the Dabie Mountains, China. Fluid inclusions from 0.003 μm to 0.78 μm in size occur in jadeite and quartz crystals, and a small number of fluid inclusions from 0.001 μm to 0.25 μm have also been detected in symplectite-forming minerals. Most of the fluid inclusions have round or negative crystal morphology and contain aqueous fluids, but some contain CO₂-rich fluids. They are usually connected to dislocations undetectable at an optical scale. The dislocations represent favorable paths for fluid leakage, accounting for non-decrepitation of most fluid inclusions when external pressure decreased at later stages, although there was partial decrepitation of some fluid inclusions unconnected to defect microstructures resulting from internal overpressure. Non-decrepitation and partial decrepitation of fluid inclusions resulted in changes of original composition and/or density. It is clear that identification of hidden re-equilibration features has significant implications for the petrological interpretation of post-peak metamorphic processes. Micro-FTIR results show that all jadeite and quartz samples contain structural water occurring as hydroxyl ions (OH⁻) and free water (H₂O) in the form of clusters of water molecules. The H₂O transformed from OH⁻ during exhumation and could have triggered and enhanced early retrograde metamorphism of the host rocks and facilitated plastic deformation of jadeite and quartz grains by dislocation movement, and thus the H₂O released during decompression might represent early-stage retrograde metamorphic fluid. The nominally anhydrous mineral (NAM) jadeite is able to transport aqueous fluids in concentrations of at least several hundred ppm water along a subduction zone to mantle depths in the form of clusters of water molecules and hydroxyl ions within crystals.     

First tectonic-geomorphology study along the Longmu–Gozha Co fault system,Western Tibet

The Longmu–Gozha Co left-lateral strike-slip fault system (LGCF) is located in remote western Tibet, forming a triple junction with both the Altyn Tagh fault (ATF) and the Karakorum fault (KF), the two major strike-slip faults in the region. The Ashikule, Gozha Co and Longmu Co faults are clear and distinct left-stepping en-echelon faults, together forming the LGCF system. Although poorly documented, quantifying its activity remains a key problem to understand the kinematics and the tectonic history of the westernmost Tibetan Plateau. Indeed, the Karakax fault (NW segment of the ATF), LGCF and KF together control the tectonics of western Tibet which itself controls the extrusion of Tibet towards the east, with the LGCF acting as a natural boundary for eastward motion of the Tibetan Plateau due to India's northward impingement. The LGCF system shows clear and impressive morphological indications of left-lateral active shear, that we quantify using field measurements (terrestrial LIDAR) along with ¹⁰Be surface-exposure dating. Our data suggest a slip-rate < 3 mm/yr, consistent with geodetic and block model studies. While it is on the order of the Karakax fault slip-rate (~ 2 mm/yr), it is smaller than those along the ATF and KF (> 9 and > 8 mm/yr, respectively), yielding a few mm/yr of extension accommodated most likely in the Ashikule graben and surroundings, located between the ATF and Karakax faults. Numerous evidences of recent tectonic-related events are present in the vicinity, such as the 1951 volcanic eruption as well as the 2008 and 2014 Ms 7.3 Yutian earthquakes, attesting of its high activity. In addition, the LGCF's en-echelon geometry and identical direction with the ATF, as well as smaller geological offsets and lower slip-rate compared to those on the surrounding faults, suggest that this segment of the ATF may be the most recent.     

The Guarani Aquifer System: estimation of recharge along the Uruguay–Brazil border

The cities of Rivera and Santana do Livramento are located on the outcropping area of the sandstone Guarani Aquifer on the Brazil–Uruguay border, where the aquifer is being increasingly exploited. Therefore, recharge estimates are needed to address sustainability. First, a conceptual model of the area was developed. A multilayer, heterogeneous and anisotropic groundwater-flow model was built to validate the conceptual model and to estimate recharge. A field campaign was conducted to collect water samples and monitor water levels used for model calibration. Field data revealed that there exists vertical gradients between confining basalts and underlying sandstones, suggesting basalts could indirectly recharge sandstone in fractured areas. Simulated downward flow between them was a small amount within the global water budget. Calibrated recharge rates over basalts and over outcropping sandstones were 1.3 and 8.1% of mean annual precipitation, respectively. A big portion of sandstone recharge would be drained by streams. The application of a water balance yielded a recharge of 8.5% of average annual precipitation. The numerical model and the water balance yielded similar recharge values consistent with determinations from previous authors in the area and other regions of the aquifer, providing an upper bound for recharge in this transboundary aquifer.