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.     

Structure, thermodynamics, and diffusion in CaAl2Si2O8 liquid from first-principles molecular dynamics

We have performed first-principles molecular dynamics simulations of CaAl₂Si₂O₈ (anorthite) liquid at pressures up to 120 GPa and temperatures of 3000, 4000 and 6000 K. At the lowest degrees of compression the liquid is seen to accommodate changes in density through decreasing the abundance of 3- and 4-membered rings, while increases in coordination of network forming cations take effect at somewhat higher degrees of compression. Results are fit to a fundamental thermodynamic relation with 4th order finite strain and 1st order thermal variable expansions. Upon compression by a factor of two, the Grüneisen parameter (γ) is found to increase continuously from 0.35 to 1.10. Weak temperature dependence in γ is thermodynamically consistent with a slight decrease in isochoric heat capacity (C_V), for which values of between 4.4 and 5.2 Nk_B are obtained, depending on the temperature. Pressure and temperature dependence of self-diffusivities is found to be well represented by an Arrhenius relation, except at 3000 K and pressures lower than 5 GPa, where self-diffusivities of Si, Al, and O increase with pressure. Analysis of the lifetimes of individual coordination species reveals that this phenomenon arises due to the disproportionately high stability of 4-fold coordinated Si, and to a lesser extent 4-fold coordinated Al. Our results represent a marked improvement in accuracy and reliability in describing the physics of CaAl₂Si₂O₈ liquid at deep mantle pressures, pointing the way to a general thermodynamic model of melts at extreme pressures and temperatures relevant to planetary-scale magma oceans and deep mantle partial melting.     

Melt extraction pathways and stagnation depths beneath the Madeira and Desertas rift zones (NE Atlantic) inferred from barometric studies

The Madeira and Desertas Islands (eastern North Atlantic) show well-developed rift zones which intersect near the eastern tip of Madeira (São Lourenço peninsula). We applied fluid inclusion barometry and clinopyroxene-melt thermobarometry to reconstruct levels of magma stagnation beneath the two adjacent rifts and to examine a possible genetic relationship during their evolution. Densities of CO₂-dominated fluid inclusions in basanitic to basaltic samples from São Lourenço yielded frequency maxima at pressures of 0.57–0.87 GPa (23–29 km depth) and 0.25–0.32 GPa (8–10 km), whereas basanites, basalts and xenoliths from the Desertas indicate 0.3–0.72 GPa (10–24 km) and 0.07–0.12 GPa (2–3 km). Clinopyroxene-melt thermobarometry applied to Ti-augite phenocryst rim and glass/groundmass compositions indicates pressures of 0.45–1.06 GPa (15–35 km; São Lourenço) and 0.53–0.89 GPa (17–28 km; Desertas Islands) which partly overlap with pressures indicated by fluid inclusions. We interpret our data to suggest a multi-stage magma ascent beneath the Madeira Archipelago: main fractionation occurs at multiple levels within the mantle (>15 km depth) and is followed by temporary stagnation within the crust prior to eruption. Depths of crustal magma stagnation beneath São Lourenço and the Desertas differ significantly, and there is no evidence for a common shallow magma reservoir feeding both rift arms. We discuss two models to explain the relations between the two adjacent rift systems: Madeira and the Desertas may represent either a two-armed rift system or two volcanic centres with separate magma supply systems. For petrological and volcanological reasons, we favour the second model and suggest that Madeira and the Desertas root in distinct regions of melt extraction. Magma focusing into the Desertas system off the hotspot axis may result from lithospheric bending caused by the load of the Madeira and Porto Santo shields, combined with regional variations in melt production due to an irregularly shaped plume.Electronic Supplementary Material Supplementary material is available for this article if you access the article at . A link in the frame on the left on that page takes you directly to the supplementary material.Editorial responsibility: J. Hoefs     

Recent landslide activity in Manaihan,East Belgium

Past landslides have been recognized in the Battice area in E-Belgium. In contrast to the other inactive landslides, the Manaihan landslide responded immediately to heavy rainfall events in the last two decades. This study aims to map its spatial extent and the dominant surface features; to measure surface displacement using GPS; to investigate subsurface structure with Cone penetration test (CPT) and corings; and to determine the depth of the shear surface by inclinometers. Results show a partial landslide reactivation. Surface velocities range between 20 and 40 cm/year and are strongly dependent on winter rainfall. CPT results give clear boundaries between the landslide mass and the undisturbed bedrock in the head scarp. Distinct shear surfaces have been determined with displacement rates up to 15.8 mm in 21 days. Further research should apply geophysical methods for two-dimensional information on the ground, investigate geotechnical properties of the landslide mass, model slope instability, and determine the influence of a sewage pipe crossing the central landslide mass as a potential cause for landslide activity.     

Extremely slow slope movements influencing the stability of Spis Castle,UNESCO site

Spis Castle, a monument included in the UNESCO World Heritage Site list (Eastern Slovakia) is built on a travertine mound overlying soft Paleogene rocks. Lateral spreading resulting from the subsidence of strong upper travertine into soft claystone strata has fractured and separated the castle rock into several cliffs. The differential movement of individual cliff faces is the primary influence on the stability of the monument. In order to monitor and quantify the movement, two techniques were adopted: a mechanical-optical TM-71 crack gauge and a demec gauge (demountable mechanical—SOMET type crack gauge). This paper presents the results and interpretation of medium and short-term monitoring at the site.     

Carbon isotope stratigraphy of Lochkovian to Eifelian limestones from the Devonian of central and southern Europe

Lower to Middle Devonian carbonates of the Prague Syncline, the Carnic Alps, the Montagne Noire, and the Cantabrian Mountains were investigated for δ¹³C_carb and δ¹³C_org. These values were measured on bulk rocks, selected components and cements. Many carbonates exhibit primary marine values, but some are altered by diagenesis. A δ¹³C curve can be presented for the latest Pridolian to Emsian time interval. Several sharp or broad positive excursions are obvious in the woschmidti-postwoschmidti, sulcatus, kitabicus, Late serotinus, and kockelianus conodont zones. The excursion at the Silurian–Devonian boundary is known worldwide and therefore considered global in nature. Some of the others are described for the first time from central and southern Europe, and their global nature has to be verified by further investigations in other regions. Most excursions relate to and/or started during major regressions whereas sea-level highstands correspond to minimal δ¹³C values. Similar relationships between sea-level changes and δ¹³C have been observed from other early Palaeozoic intervals. The transgressive Chote? (?) and Ka?ák events are marked by positive isotope excursions, this type of combination is usually observed in late Palaeozoic to Cenozoic black shale events.     

Spatial correlation of deformation and mineral reaction in experimentally deformed plagioclase–olivine aggregates

Shear deformation of hot pressed plagioclase–olivine aggregates was studied in the presence and absence of mineral reaction. Experiments were performed at 900 °C, 1500 MPa, and a constant shear strain rate of 5×10⁻⁵ s⁻¹ in a solid medium apparatus. Whether the mineral reaction between plagioclase and olivine takes place or not is controlled by choosing the appropriate plagioclase composition; labradorite (An₆₀) does not react, anorthite (An₉₂) does. Labradorite–olivine aggregates deformed without reaction are very strong and show strain hardening throughout the experiment. Syndeformational reaction between olivine and anorthite causes a pronounced strain weakening. The reaction produces fine-grained opx–cpx–spinel aggregates, which accommodate a large fraction of the finite strain. Deformation and reaction are localised within a 0.5-mm-wide sample. Three representative samples were analysed for their fabric anisotropy R* and shape-preferred orientation α* (fabric angle with the shear plane) using the autocorrelation function (ACF). Fabric anisotropy can be calibrated to quantify strain variations across the sheared samples. In the deformed and reacted anorthite–olivine aggregate, there is a strong correlation between reaction progress and strain; regions of large shear strain correspond to regions of maximum reaction progress. Within the sample, the derived strain rate variations range up to almost one order of magnitude.     

Alternative water management options to reduce vulnerability for climate change in the Netherlands

Urbanization, land subsidence and sea level rise will increase vulnerability of the urbanized low-lying areas in the western part of the Netherlands. In this article possibilities are explored to reduce vulnerability of these areas by implementing alternative water management options. Two main water management fields are distinguished, water supply and flood control. A four-component vulnerability framework is presented that includes threshold capacity, coping capacity, recovery capacity, and adaptive capacity. By using the vulnerability framework it is shown that current water supply and flood control strategies in the Netherlands focus on increasing threshold capacity by constructing higher and stronger dikes, improved water storage and delivery infrastructure. A complete vulnerability decreasing strategy requires measures that include all four capacities. Flood damage reduction, backup water supply systems and emergency plans are measures that can contribute to increasing coping capacity. Recovery capacity can be increased by multi-source water supply, insurance, or establishing disaster funds. Adaptive capacity can be developed by starting experiments with new modes of water supply and urbanization. Including all four components of the vulnerability framework enables better understanding of water and climate related vulnerability of urban areas and enables developing more complete water management strategies to reduce vulnerability.