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.     

An Elasto-Plastic Constitutive Model for Rock Joints Under Cyclic Loading and Constant Normal Stiffness Conditions

An elasto-plastic constitutive model is introduced for rock joints under cyclic loading, considering the additional shear resistance generated by the asperity damage in the first forward shear cycle and sliding mechanism for further shearing. A series of cyclic loading direct shear tests was conducted on artificial joints with triangular asperities and replicas of a real rock asperity surface under constant normal stiffness (CNS) conditions. The model was calibrated and then validated using selected data sets from the experimental results. Model simulations were found to be in good agreement with the rock joints behaviour under cyclic loading and CNS conditions both in stress prediction and dilation behaviour. In addition, dynamic stability analysis of an underground structure was carried out, using Universal Distinct Element Code and the proposed constitutive model.     

Evidence for fullerenes in solid bitumen from pillow lavas of Proterozoic age from Mítov (Bohemian Massif, Czech Republic)

Andesitic pillow lavas containing biogenic, solid bitumen (SB) are a constituent of a Neoproterozoic volcanosedimentary sequence (Teplá-Barrandian unit, Bohemian Massif) in the Mítov area of the Czech Republic. A black shale formation that is crosscut by these andesitic basalts is 565 Ma old. Carbon disulfide extracts of two powdered samples of SB contain 0.2 and 0.3 ppm of C₆₀, respectively, as determined by high-pressure liquid chromatography. The peak assignment based on retention time is fully supported by high-resolution electron ionization mass spectrometry (EI-MS). No C₇₀ was detected, nor was C₆₀ found in two other SB samples from this locality. Other investigated carbonaceous samples from Bohemia (coals and anthracites of Upper Paleozoic age and anthraxolite, graphitoids, and graphite of Upper Proterozoic age) did not contain fullerenes at concentrations above the detection limit of 0.01 ppm. The absence of C₆₀ in these samples was confirmed by EI-MS. The proposed mechanism of fullerene formation involves a primary algal phase, generation of a hydrocarbonaceous mixture in the course of thermal evolution of the sedimentary series, and their high-temperature transformation related to the extrusion of basalt. An important feature for fullerene conservation was the enclosure of fullerenes in SB with a structure similar to glasslike carbon, where the fullerene was protected against oxidation.     

Review of ray-Born forward modeling for migration and diffraction analysis

The ray-Born approximation is a very useful tool for forward modeling of scattered waves. The fact that ray-Born modeling underlies most seismic migration techniques, and therefore shares their assumptions, is a justification in itself to consider it for forward modeling. The ray-Born approximation does not make an explicit distinction between specular reflections and nonspecular diffractions. It therefore allows the modeling of diffractions from structural discontinuities such as edges and tips, as well as caustic diffractions. In the simplest implementation ray-Born seismograms are multiple-free. Ray-Born modeling can be orders of magnitude faster than finite-difference modeling, both in two-and three dimensions.     

Combining long- and short-term probabilistic volcanic hazard assessment with cost-benefit analysis to support decision making in a volcanic crisis from the Auckland Volcanic Field,New Zealand

By using BET_VH, we propose a quantitative probabilistic hazard assessment for base surge impact in Auckland, New Zealand. Base surges resulting from phreatomagmatic eruptions are among the most dangerous phenomena likely to be associated with the initial phase of a future eruption in the Auckland Volcanic Field. The assessment is done both in the long-term and in a specific short-term case study, i.e. the simulated pre-eruptive unrest episode during Exercise Ruaumoko, a national civil defence exercise. The most important factors to account for are the uncertainties in the vent location (expected for a volcanic field) and in the run-out distance of base surges. Here, we propose a statistical model of base surge run-out distance based on deposits from past eruptions in Auckland and in analogous volcanoes. We then combine our hazard assessment with an analysis of the costs and benefits of evacuating people (on a 1 × 1-km cell grid). In addition to stressing the practical importance of a cost-benefit analysis in creating a bridge between volcanologists and decision makers, our study highlights some important points. First, in the Exercise Ruaumoko application, the evacuation call seems to be required as soon as the unrest phase is clear; additionally, the evacuation area is much larger than what is recommended in the current contingency plan. Secondly, the evacuation area changes in size with time, due to a reduction in the uncertainty in the vent location and increase in the probability of eruption. It is the tradeoff between these two factors that dictates which cells must be evacuated, and when, thus determining the ultimate size and shape of the area to be evacuated.     

The role of long‐term human impact on avulsion and fan development

This study aims to understand (mainly qualitatively) the long‐term role of human impact on avulsion processes and the development of fluvial (mega‐) fans in semi‐arid environments. In this paper we refer to human impact as the direct influences of actions on the river's hydraulics (i.e. flow regulation, flow diversion and channel engineering). In five case‐studies drawn from the Khuzestan plains in southwest Iran we have analysed the setup and triggering conditions of specific avulsions that occurred in the past (timescale of millennia) and identified the role of human interference in their causation. Our analysis is based on the integration of historical, archaeological, geomorphological and geological data. Through this study we demonstrate that avulsions in the Khuzestan plains are the result of long‐term and complex interplay between multiple human‐induced and natural causes. In similar ways human‐induced actions may play important roles during different phases of avulsion development. The ‘success‘ of an avulsion in the post‐triggering phase may be defined by human‐induced setup causes as well as morphodynamic processes. We suggest that present‐day flood events may be partly inherited from long‐term human alterations of the natural processes. These finding could have implications for any fluvial system (e.g. distributive fluvial systems, deltas) where avulsion plays a major role in their development and research tends to emphasize on natural mechanisms. Copyright © 2016 John Wiley & Sons, Ltd.     

Quality and timing of crowd-based water level class observations

Crowd-based hydrological observations can supplement existing monitoring networks and allow data collection in regions where otherwise no data would be available. In the citizen science project CrowdWater, repeated water level observations using a virtual staff gauge approach result in time series of water level classes (WL-classes). To investigate the quality of these observations, we compared the WL-class data with “real” (i.e., measured) water levels from the same stream at a nearby gauging station. We did this for nine locations where citizen scientists reported multiple observations using a smartphone app and at 12 locations where signposts were set up to ask citizens to record observations on a paper form that could be left in a letterbox. The results indicate that the quality of the data collected with the app was better than for the forms. A possible explanation is that for each app location, a single person submitted the vast majority of the observations, whereas at the locations of the forms almost every observation was made by a different person. On average, there were more contributions between May and September than during the other months. Observations were submitted for a range of flow conditions, with a higher fraction of high flow observations for the locations were data were collected with the app. Overall, the results are encouraging for citizen science approaches in hydrology and demonstrate that the smartphone application and the virtual staff gauge are a promising approach for crowd-based water level class observations.     

Short-term water quality variable prediction using a hybrid CNN–LSTM deep learning model

Stochastic Environmental Research and Risk Assessment - Water quality monitoring is an important component of water resources management. In order to predict two water quality variables, namely...     

Real-time envelope cross-correlation detector: application to induced seismicity in the Insheim and Landau deep geothermal reservoirs

We develop and test a real-time envelope cross-correlation detector for use in seismic response plans to mitigate hazard of induced seismicity. The incoming seismological data are cross-correlated in real-time with a set of previously recorded master events. For robustness against small changes in the earthquake source locations or in the focal mechanisms we cross-correlate the envelopes of the seismograms rather than the seismograms themselves. Two sequenced detection conditions are implemented: After passing a single trace cross-correlation condition, a network cross-correlation is calculated taking amplitude ratios between stations into account. Besides detecting the earthquake and assigning it to the respective reservoir, real-time magnitudes are important for seismic response plans. We estimate the magnitudes of induced microseismicity using the relative amplitudes between master event and detected event. The real-time detector is implemented as a SeisComP3 module. We carry out offline and online performance tests using seismic monitoring data of the Insheim and Landau geothermal power plants (Upper Rhine Graben, Germany), also including blasts from a nearby quarry. The comparison of the automatic real-time catalogue with a manually processed catalogue shows, that with the implemented parameters events are always correctly assigned to the respective reservoir (4 km distance between reservoirs) or the quarry (8 km and 10 km distance, respectively, from the reservoirs). The real-time catalogue achieves a magnitude of completeness around 0.0. Four per cent of the events assigned to the Insheim reservoir and zero per cent of the Landau events are misdetections. All wrong detections are local tectonic events, whereas none are caused by seismic noise.     

The intensity of the earth's magnetic field in the past derived from the archaeomagnetic data

a n¶rt;u¶rt; amuu amua uuu anmuaum n a n¶rt;u 8500 m nm um au aam m uuu m naama. ¶rt;u u ¶rt;a ¶rt; u ¶rt; m¶rt; mumu auu nau nuu aau mama [1–3] (Puc. 1.B). nma aau auau (Puc.2) mnaua m m m¶rt;a, ¶rt; au n¶rt; amu u, m n¶rt;u 2- ma m, mmu naa auu nu¶rt; n¶rt;a 1000 m u 350 m, au a aumu, mmm 80%- mmu. am au ¶rt;a u anmu ¶rt; m¶rt; mumu (mum) naa auu u¶rt; ma u ¶rt; m naama[5] (Puc. 3). uma a mam nma aaua naaa auu nu¶rt; n¶rt;a 750 m, 200 m u a — 300 m. (Puc. 4.) nmu u ¶rt;a nma amua an¶rt;u n¶rt;u n u ma m (au) auumu m ¶rt;m m (Puc. 5). aa a m¶rt;m nu naamaum n aam ¶rt;uu mu au, anum¶rt;a m uua nm m¶rt;a.

---

---

Dedicated to Academician Alois Zátopek on His 65th Birthday