Stability at high pressure, elastic behavior and pressure-induced structural evolution of “Al5BO9”, a mullite-type ceramic material

Elastic behavior and pressure-induced structural evolution of synthetic boron-mullite “Al₅BO₉” (a = 5.678(2) Å, b = 15.015(4) Å and c = 7.700(3) Å, space group Cmc2₁, Z = 4) were investigated up to 7.4 GPa by in situ single-crystal X-ray diffraction with a diamond anvil cell under hydrostatic conditions. No phase transition or anomalous compressional behavior occurred within the investigated P range. Fitting the P–V data with a truncated second-order (in energy) Birch-Murnaghan Equation-of-State (BM-EoS), using the data weighted by the uncertainties in P and V, we obtained: V ₀ = 656.4(3) Å³ and K _T0 = 165(7) GPa (β _V0 = 0.0061(3) GPa^?1). The evolution of the Eulerian finite strain versus normalized stress (f _E–F _E plot) leads to an almost horizontal trend, showing that a truncated second-order BM-EoS is appropriate to describe the elastic behavior of “Al₅BO₉” within the investigated P range. The weighted linear regression through the data points gives: F _E(0) = 159(11) GPa. Axial compressibility coefficients yielded: β _a  = 1.4(2) × 10^?3 GPa^?1, β _b  = 3.4(4) × 10^?3 GPa^?1, and β _c  = 1.7(3) × 10^?3 GPa^?1 (β _a :β _b :β _c  = 1:2.43:1.21). The highest compressibilities observed in this study within (100) can be ascribed to the presence of voids represented by five-membered rings of polyhedra: Al1–Al3–Al4–Al1–Al3, which allow accommodating the effect of pressure by polyhedral tilting. Polyhedral tilting around the voids also explains the higher compressibility along [010] than along [001]. The stiffer crystallographic direction observed here might be controlled by the infinite chains of edge-sharing octahedra running along [100], which act as “pillars”, making the structure less compressible along the a-axis than along the b- and c-axis. Along [100], compression can only be accommodated by deformation of the edge-sharing octahedra (and/or by compression of the Al–O bond lengths), as no polyhedral tilting can occur. In addition, a comparative elastic analysis among the mullite-type materials is carried out.     

Single crystal U-Pb zircon age and Sr-Nd isotopic composition of impactites from the Bosumtwi impact structure, Ghana: Comparison with country rocks and Ivory Coast tektites

The 1.07?Myr old Bosumtwi impact structure (Ghana), excavated in 2.1-2.2?Gyr old supracrustal rocks of the Birimian Supergroup, was drilled in 2004. Here, we present single crystal U-Pb zircon ages from a suevite and two meta-graywacke samples recovered from the central uplift (drill core LB-08A), which yield an upper Concordia intercept age of ca. 2145?±?82?Ma, in very good agreement with previous geochronological data for the West African Craton rocks in Ghana. Whole rock Rb-Sr and Sm-Nd isotope data of six suevites (five from inside the crater and one from outside the northern crater rim), three meta-graywacke, and two phyllite samples from core LB-08A are also presented, providing further insights into the timing of the metamorphism and a possibly related isotopic redistribution of the Bosumtwi crater rocks. Our Rb-Sr and Sm-Nd data show also that the suevites are mixtures of meta-greywacke and phyllite (and possibly a very low amount of granite). A comparison of our new isotopic data with literature data for the Ivory Coast tektites allows to better constrain the parent material of the Ivory Coast tektites (i.e., distal impactites), which is thought to consist of a mixture of metasedimentary rocks (and possibly granite), but with a higher proportion of phyllite (and shale) than the suevites (i.e., proximal impactites). When plotted in a Rb/Sr isochron diagram, the sample data points (n?=?29, including literature data) scatter along a regression line, whose slope corresponds to an age of 1846?±?160?Ma, with an initial Sr isotope ratio of 0.703?±?0.002. However, due to the extensive alteration of some of the investigated samples and the lithological diversity of the source material, this age, which is in close agreement with a possible "metamorphic age" of ～?1.8-1.9?Ga tentatively derived from our U-Pb dating of zircons, is difficult to consider as a reliable metamorphic age. It may perhaps reflect a common ancient source whose Rb-Sr isotope systematics has not basically been reset on the whole rock scale during the Bosumtwi impact event, or even reflect another unknown geologic event.     

The role of the Kupferschiefer in the formation of hydrothermal base metal mineralization in the Spessart ore district, Germany: insight from detailed sulfur isotope studies

The Spessart district (SW Germany), located at the southwestern margin of the Permian Kupferschiefer basin in Central Europe, hosts abundant stratabound and structurally controlled base metal mineralization. The mineralization styles identified are (1) stratabound Cu-Pb-Zn-(Ag) ores in Zechstein sedimentary rocks, (2) structurally controlled Cu-As-(Ag) ores in Zechstein sedimentary rocks, (3) crosscutting Co-Ni-(Bi)-As and Cu-Fe-As veins, (4) stratabound metasomatic Fe-Mn carbonate ores in Zechstein dolomite, (5) barren barite veins, and (6) Fe-Mn-As veins in Permian rhyolites. Building on previous work that involved mineralogical, textural, and chemical characterization of the major mineralization types, we have performed a comprehensive sulfur isotope study that applied both conventional and novel laser-ablation multi-collector inductively coupled plasma mass spectrometry techniques. The δ³⁴S values of sulfide minerals from the different ore types are consistently negative and highly variable, in the range between −44.5‰ and −3.9‰, whereas the δ³⁴S values of barite are all positive in the range between 4.7‰ and 18.9‰. Remarkably, stratabound and structurally controlled mineralization in Zechstein sedimentary rocks has the least negative δ³⁴S values, whereas vein-type deposits have consistently more negative δ³⁴S values. The observed pattern of sulfide δ³⁴S values can be best interpreted in terms of fluid mixing at the basement-cover interface. Hydrothermal fluids originating from the crystalline basement migrated upward along subvertical fault zones and were periodically injected into groundwaters that were flowing in the post-Variscan sedimentary cover. These groundwaters had interacted with the Zechstein sedimentary rocks, resulting in fluids characterized by elevated concentrations of reduced sulfur (with negative δ³⁴S values) and alkaline pH. Repeated mixing between both chemically contrasting fluids caused rapid and efficient precipitation of sulfide ore minerals in hydrothermal veins with highly variable but distinctly negative δ³⁴S values.     

Radial distribution of lead and lead isotopes in stem wood of Norway spruce: A reliable archive of pollution trends in Central Europe

Annual growth rings of a common hardwood species, Picea abies L., were investigated as a potential archive of past atmospheric Pb pollution. Wide distribution of trees in terrestrial settings and straightforward chronology are two advantages of this potential geochemical archive, but several processes described in the literature may obscure the trends in past Pb deposition. These confounding factors include, e.g., radial post-depositional mobility of Pb in xylem, and ecosystem acidification leading to higher bioavailability of Pb. One- to five-year annual wood increments were analyzed for Pb concentrations and ²⁰⁶Pb/²⁰⁷Pb ratios at Jezeri (JEZ), Uhlirska (UHL) and Na Lizu (LIZ), three sites in the Czech Republic, differing in atmospheric Pb loads. Three to four trees per site were included in the study. Distinct Pb concentration maxima between 1960 and 1990 at the two heavily polluted sites (JEZ and UHL) coincided with historical Pb emissions known from inventories of industrial production. No Pb concentration maxima were found at one site, LIZ, situated in a national park 150 km from major pollution sources. Spruce tree rings from JEZ, located just 5 km from coal-burning power stations, contained a large proportion of coal-derived Pb (a high-²⁰⁶Pb/²⁰⁷Pb ratio of 1.19). A coal-related maximum in ²⁰⁶Pb/²⁰⁷Pb in JEZ tree rings was found using two different analytical techniques, laser-ablation multi-collector ICP MS, and single-collector sector-field ICP MS. In a three-isotope graph (²⁰⁶Pb/²⁰⁷Pb vs. ²⁰⁸Pb/²⁰⁷Pb), tree-ring data plotted into the field of ombrotrophic (i.e., rain-fed) peat bogs, suggesting negligible contribution of bedrock-derived Pb in the xylem. We concluded that none of the potential confounding factors played a major role at our sites. Annual growth rings of P. abies in Central Europe faithfully recorded historical changes in atmospheric Pb depositions.     

Dilation and Spalling in Axially Compressed Beams Subjected to Bending

Laboratory testing of rectangular beams using a synthetic rock was used to investigate the onset of dilation and spalling. The beams are axially compressed and subjected to 4-point bending to provide non-uniform compressive stresses. The maximum tangential stress occurs at the top of the beam and rapidly decreases with distance from the top of the beam. This stress distribution was used to simulate the maximum tangential stress distribution found around circular excavations. The results showed using this beam test configuration that the onset of dilation based on beam displacement and visually observed spalling began at approximately the same stress level. Discrete element numerical analyses (particle flow code) were used to evaluate the stress path at various locations in the beams. The analyses revealed that spalling and dilation in the beams occurred well below the peak strength failure envelope determined from conventional laboratory tests. The findings suggest that the onset of dilation in laboratory tests appears to be a good indicator for assessing the stress magnitudes required to initiate spalling.     

Behavior of trace elements in relation to Lu–Hf and Sm–Nd geochronometers during metamorphic dehydration–hydration in the HP domain of Vårdalsneset, Western Gneiss Region, Norway

The geochemical and isotopic characterization of an eclogite and the associated retrogressive amphibolite at Vårdalsneset, WGR, Norwegian Caledonide was undertaken to investigate the mobility of REE and Hf and the behavior of Lu–Hf and Sm–Nd geochronometers during metamorphic dehydration/rehydration. Eclogitic garnets display a distinct core–rim chemical zoning. Thermodynamic modeling indicates that both cores (13–22 kbar, 500–580°C) and rims (>16 kbar, 610–660°C) crystallized under eclogite-facies conditions. The core–rim zoning corresponds to the dehydration of the system. This petrographic disequilibrium is associated with Lu–Hf and Sm–Nd disequilibrium, which prevents dating of the eclogitic stages. At the rock scale, the incoming fluid responsible for eclogite–amphibolite retrogression brought in Sm and Nd, leached Lu, and had no influence on Hf. At the grain scale, mass balance shows that Sm and Nd were stored in clinozoisite since the first eclogitic stage, whereas Lu and Hf, which were more thoroughly redistributed among minerals during retrogression, enable the dating of the amphibolitic facies at 378 ± 17 Ma.     

Fragment properties at the catastrophic disruption threshold: The effect of the parent body’s internal structure

Numerical simulations of asteroid breakups, including both the fragmentation of the parent body and the gravitational interactions between the fragments, have allowed us to reproduce successfully the main properties of asteroid families formed in different regimes of impact energy, starting from a non-porous parent body. In this paper, using the same approach, we concentrate on a single regime of impact energy, the so-called catastrophic threshold usually designated by , which results in the escape of half of the target’s mass. Thanks to our recent implementation of a model of fragmentation of porous materials, we can characterize for both porous and non-porous targets with a wide range of diameters. We can then analyze the potential influence of porosity on the value of , and by computing the gravitational phase of the collision in the gravity regime, we can characterize the collisional outcome in terms of the fragment size and ejection speed distributions, which are the main outcome properties used by collisional models to study the evolutions of the different populations of small bodies. We also check the dependency of on the impact speed of the projectile.In the strength regime, which corresponds to target sizes below a few hundreds of meters, we find that porous targets are more difficult to disrupt than non-porous ones. In the gravity regime, the outcome is controlled purely by gravity and porosity in the case of porous targets. In the case of non-porous targets, the outcome also depends on strength. Indeed, decreasing the strength of non-porous targets make them easier to disrupt in this regime, while increasing the strength of porous targets has much less influence on the value of . Therefore, one cannot say that non-porous targets are systematically easier or more difficult to disrupt than porous ones, as the outcome highly depends on the assumed strength values. In the gravity regime, we also confirm that the process of gravitational reaccumulation is at the origin of the largest remnant’s mass in both cases. We then propose some power-law relationships between and both target’s size and impact speed that can be used in collisional evolution models. The resulting fragment size distributions can also be reasonably fitted by a power-law whose exponent ranges between −2.2 and −2.7 for all target diameters in both cases and independently on the impact velocity (at least in the small range investigated between 3 and 5 km/s). Then, although ejection velocities in the gravity regime tend to be higher from porous targets, they remain on the same order as the ones from non-porous targets.     

Penetrometry of granular and moist planetary surface materials: Application to the Huygens landing site on Titan

The Huygens probe landed on the then unknown surface of Titan in January 2005. A small, protruding penetrometer, part of the Surface Science Package (SSP), was pushed into the surface material measuring the mechanical resistance of the ground as the probe impacted the landing site. We present laboratory penetrometry into room temperature surface analogue materials using a replica penetrometer to investigate further the nature of Titan’s surface and examine the sensor’s capabilities. The results are then compared to the flight instrument’s signature and suggest the Titan surface substrate material consists of sand-sized particles with a mean grain size ～2 mm. A possible thin 7 mm coating with mechanical properties similar to terrestrial snow may overlie this substrate, although due to the limited data we are unable to detect any further layering or grading within the near-surface material. The unusual weakening with depth of the signature returned from Titan has, to date, only been reproduced using a damp sand target that becomes progressively wetter with depth, and supports the suggestion that the surface may consist of a damp and cohesive material with interstitial liquid contained between its grains. Comparison with terrestrial analogues highlights the unusual nature of the landing site material.