Radio-colouration of diamond: a spectroscopic study

We have undertaken a study of the common green or orange-brown spots at the surface of rough diamond specimens, which are caused by alpha particles emanating from radioactive sources outside the diamond. Richly coloured haloes represent elevated levels of structural damage, indicated by strong broadening of the main Raman band of diamond, intense strain birefringence, and up-doming of spots due to their extensive volume expansion. Green radio-colouration was analogously generated through the irradiation of diamond with 8.8 MeV helium ions. The generation of readily visible radio-colouration was observed after irradiating diamond with ≥10¹⁵ He ions per cm². The accumulation of such a high number of alpha particles requires irradiation of the diamond from a radioactive source over long periods of time, presumably hundreds of millions of years in many cases. In the samples irradiated with He ions, amorphisation was observed in volume areas where the defect density exceeded 5 × 10^?3 Å^?3 (or 0.03 dpa; displacements per target atom). In contrast, graphitisation as a direct result of the ion irradiation was not observed. The green colouration transformed to brown at moderate annealing temperatures (here 450 °C). The colour transformation is associated with only partial recovery of the radiation damage. The colour change is mainly due to the destruction of the GR1 centre, explained by trapping of vacancies at A defects to form the H3 centre. An activation energy of ~2.4 ± 0.2 eV was determined for the GR1 reduction. The H3 centre, in turn, causes intense yellowish-green photoluminescence under ultraviolet illumination. Radio-colouration and associated H3 photoluminescence are due to point defects created by the ions irradiated, whereas lattice ionisation is of minor importance. This is concluded from the depth distribution of the colouration and the photoluminescence intensity (which corresponds to the defect density but not the ionisation distribution pattern). The effect of the implanted He ions themselves on the colour and photoluminescence seems to be negligible, as radio-colouration and H3 emission were analogously produced through irradiation of diamond with C ions. The photoluminescence emission becomes observable at extremely low defect densities on the order of 10^?6 Å^?3 (or 0.000006 dpa) and is suppressed at moderate defect densities of ~5 × 10^?4 Å^?3 (or ~0.003 dpa). Intensely brown-coloured diamond hence does not show the H3 emission anymore. Anneals up to 1,600 °C has reduced considerably irradiation damage and radio-colouration, but the structural reconstitution of the diamond (and its de-colouration) was still incomplete.     

Reactivity of sandstone and siltstone samples from the Ketzin pilot CO2 storage site-Laboratory experiments and reactive geochemical modeling

To evaluate mineralogical-geochemical changes within the reservoir of the Ketzin pilot CO₂ storage site in Brandenburg, Germany, two sets of laboratory experiments on sandstone and siltstone samples from the Stuttgart Formation have been performed. Samples were exposed to synthetic brine and pure CO₂ at experimental conditions and run durations of 5.5 MPa/40 °C/40 months for sandstone and 7.5 MPa/40 °C/6 months for siltstone samples, respectively. Mineralogical changes in both sets of experiments are generally minor making it difficult to differentiate natural variability of the whole rock samples from CO₂-induced alterations. Results of sandstone experiments suggest dissolution of the anorthite component of plagioclase, anhydrite, K-feldspar, analcime, hematite and chlorite + biotite. Dissolution of the anorthite component of plagioclase, anhydrite and K-feldspars is also observed in siltstone experiments. In an inverse modeling approach, an extensive set of equilibrium simulations was set up in order to reproduce the experimental observations of the sandstone experiments. Simulations generally show fairly good matches with the experimental observations. Best matches with measured brine data are obtained from mineral combinations of albite, analcime, anhydrite, dolomite, hematite, illite, and kaolinite. The major discrepancies during equilibrium modeling, however, are reactions involving Fe²⁺ and Al³⁺. The best matching subsets of the equilibrium models were finally run including kinetic rate laws. These simulations reveal that experimentally determined brine data was well matched, but reactions involving K⁺ and Fe²⁺ are not fully covered. The modeling results identified key primary minerals as well as key chemical processes, but also showed that the models are not capable of covering all possible contingencies.     

Composition of impact melt particles and the effects of post‐impact alteration in suevitic rocks at the Yaxcopoil‐1 drill core,Chicxulub crater,Mexico

Abstract Petrographical and chemical analysis of melt particles and alteration minerals of the about 100 m‐thick suevitic sequence at the Chicxulub Yax‐1 drill core was performed. The aim of this study is to determine the composition of the impact melt, the variation between different types of melt particles, and the effects of post‐impact hydrothermal alteration. We demonstrate that the compositional variation between melt particles of the suevitic rocks is the result of both incomplete homogenization of the target lithologies during impact and subsequent post‐impact hydrothermal alteration. Most melt particles are andesitic in composition. Clinopyroxene‐rich melt particles possess lower SiO₂ and higher CaO contents. These are interpreted by mixing of melts from the silicate basement with overlying carbonate rocks. Multi‐stage post‐impact hydrothermal alteration involved significant mass transfer of most major elements and caused further compositional heterogeneity between melt particles. Following backwash of seawater into the crater, palagonitization of glassy melt particles likely caused depletion of SiO₂, Al₂O₃, CaO, Na₂O, and enrichment of K₂O and FeO_tot during an early alteration stage. Since glass is very susceptible to fluid‐rock interaction, the state of primary crystallization of the melt particles had a significant influence on the intensity of the post‐impact hydrothermal mass transfer and was more pronounced in glassy melt particles than in well‐crystallized particles. In contrast to other occurrences of Chicxulub impactites, the Yax‐1 suevitic rocks show strong potassium metasomatism with hydrothermal K‐feldspar formation and whole rock K₂0 enrichment, especially in the lower unit of the suevitic sequence. A late stage of hydrothermal alteration is characterized by precipitation of silica, analcime, and Na‐bearing Mg‐rich smectite, among other minerals. This indicates a general evolution from a silica‐undersaturated fluid at relatively high potassium activities at an early stage toward a silica‐oversaturated fluid at relatively high sodium activities at later stages in the course of fluid rock interaction.     

Statistical Relational Learning of Grammar Rules for 3D Building Reconstruction

The automatic interpretation of 3D point clouds for building reconstruction is a challenging task. The interpretation process requires highly structured models representing semantics. Formal grammars can describe structures as well as the parameters of buildings and their parts. We propose a novel approach for the automatic learning of weighted attributed context‐free grammar rules for 3D building reconstruction, supporting the laborious manual design of rules. We separate structure from parameter learning. Specific Support Vector Machines (SVMs) are used to generate a weighted context‐free grammar and predict structured outputs such as parse trees. The grammar is extended by parameters and constraints, which are learned based on a statistical relational learning method using Markov Logic Networks (MLNs). MLNs enforce the topological and geometric constraints. MLNs address uncertainty explicitly and provide probabilistic inference. They are able to deal with partial observations caused by occlusions. Uncertain projective geometry is used to deal with the uncertainty of the observations. Learning is based on a large building database covering different building styles and façade structures. In particular, a treebank that has been derived from the database is employed for structure learning.     

Vegetation and climate history in the Laptev Sea region (Arctic Siberia) during Late Quaternary inferred from pollen records

Paleoenvironmental records from a number of permafrost sections and lacustrine cores from the Laptev Sea region dated by several methods (¹⁴C-AMS, TL, IRSL, OSL and ²³⁰Th/U) were analyzed for pollen and palynomorphs. The records reveal the environmental history for the last ca 200 kyr. For interglacial pollen spectra, quantitative temperature values were estimated using the best modern analogue method. Sparse grass-sedge vegetation indicating arctic desert environmental conditions existed prior to 200 kyr ago. Dense, wet grass-sedge tundra habitats dominated during an interstadial ca 200–190 kyr ago, reflecting warmer and wetter summers than before. Sparser vegetation communities point to much more severe stadial conditions ca 190–130 kyr ago. Open grass and Artemisia communities with shrub stands (Alnus fruticosa, Salix, Betula nana) in more protected and moister places characterized the beginning of the Last Interglacial indicate climate conditions similar to present. Shrub tundra (Alnus fruticosa and Betula nana) dominated during the middle Eemian climatic optimum, when summer temperatures were 4–5 °C higher than today. Early-Weichselian sparse grass-sedge dominated vegetation indicates climate conditions colder and dryer than in the previous interval. Middle Weichselian Interstadial records indicate moister and warmer climate conditions, for example, in the interval 40–32 kyr BP Salix was present within dense, grass-sedge dominated vegetation. Sedge-grass-Artemisia-communities indicate that climate became cooler and drier after 30 kyr BP, and cold, dry conditions characterized the Late Weichselian, ca 26–16 kyr BP, when grass-dominated communities with Caryophyllaceae, Asteraceae, Cichoriaceae, Selaginella rupestris were present. From 16 to 12 kyr BP, grass-sedge communities with Caryophyllaceae, Asteraceae, and Cichoriaceae indicate climate was significantly warmer and moister than during the previous interval. The presence of Salix and Betula reflect temperatures about 4 °C higher than present at about 12–11 kyr BP, during the Allerød interval, but shrubs were absent in the Younger Dryas interval, pointing to a deterioration of climate conditions. Alnus fruticosa, Betula nana, Poaceae, and Cyperaceae dominate early Holocene spectra. Reconstructed absolute temperature values were substantially warmer than present (up to 12 °C). Shrubs gradually disappeared from coastal areas after 7.6 kyr BP when vegetation cover became similar to modern. A comparison of proxy-based paleoenvironmental reconstructions with the simulations performed by an Earth system model of intermediate complexity (CLIMBER-2) show good accordance between the regional paleodata and model simulations, especially for the warmer intervals.     

Retention of uranium in complexly altered zircon: An example from Bancroft,Ontario

Mesoproterozoic (~ 1050 Ma; Stenian) zircon crystals from the Saranac Prospect, Bancroft, Ontario, contain up to ~ 1 wt.% U and ~ 0.15 wt.% Th and, correspondingly, they are for the most part extensively radiation-damaged (calculated total α-doses 2.3?35.3 × 10¹⁸/g). The crystals show textures of complex, intense chemical alteration that is attributed to multiple, low-T replacement events along fluid-controlled reaction fronts. Centers of crystals appear totally replaced; the primary zoning is virtually erased and the material has high porosity and numerous inclusions. Interior regions surrounding the central reworked areas still exhibit primary igneous-type zoning; in those regions the alteration emanates from fractures and then follows the more radiation-damaged growth zones. Altered areas are typically recognized by their high porosity, low BSE intensity, and deficient analytical totals. Those regions often have lost a significant fraction of their radiogenic Pb. They are in general somewhat depleted in Zr, Si, and U, and are notably enriched in Ca and Fe. Element maps reveal elevated concentrations of Al and Y within filled fractures. Our observations indicate that the fluid-driven ion exchange is mainly controlled by the accessibility of micro-areas with elevated levels of radiation damage to transporting fluids via “fast pathways”. Most importantly, there is apparent Zr?Si?U equilibrium between initially existing and newly formed zircon. The retention of U after the chemical replacement (94 ± 14% relative to the original U content in the respective zones) does not significantly fall below the retention of two major cations Zr (95 ± 4%) and Si (95 ± 2%). In spite of the partially extreme hydrothermal alteration overprinting, the original U zoning in the crystals is well preserved. These observations suggest that preferential chemical leaching of U from zircon is clearly not a general feature of this mineral. This in turn seems to question the general validity of hydrothermal experiments to low-T, fluid-driven alteration of zircon in geological environments. The observed apparent immobility of U may affect the interpretation of U?Pb discordance in zircon, and the performance assessment of this mineral as potential waste form for actinides.     

A field,laboratory, and literature review evaluation of the water retention curve of volcanic ash soils: How well do standard laboratory methods reflect field conditions?

Accurate determination of the water retention curve (WRC) of a soil is essential for the understanding and modelling of the subsurface hydrological, ecological, and biogeochemical processes. Volcanic ash soils with andic properties (Andosols) are recognized as important providers of ecological and hydrological services in mountainous regions worldwide due to their large fraction of small size particles (clay, silt, and organic matter) that gives them an outstanding water holding capacity. Previous comparative analyses of in situ (field) and standard laboratory methods for the determination of the WRC of Andosols showed contrasting results. Based on an extensive analysis of laboratory, experimental, and field measured WRCs of Andosols in combination with data extracted from the published literature we show that standard laboratory methods using small soil sample volumes (≤300 cm³) mimic the WRC of these soils only partially. The results obtained by the latter resemble only a small portion of the wet range of the Andosols' WRC (from saturation up to −5 kPa, or pF 1.7), but overestimate substantially their water content for higher matric potentials. This discrepancy occurs irrespective of site-specific land use and cover, soil properties, and applied method. The disagreement limits our capacity to infer correctly subsurface hydrological behaviour, as illustrated through the analysis of long-term soil moisture and matric potential data from an experimental site in the tropical Andes. These findings imply that results reported in past research should be used with caution and that future research should focus on determining laboratory methods that allow obtaining a correct characterization of the WRC of Andosols. For the latter, a set of recommendations and future directions to solve the identified methodological issues is proposed.     

Thermal and transport properties of mantle rock at high pressure: Applications to super-Earths

In the present study, the temperature- and pressure-dependent transport and thermal properties, i.e., viscosity, phonon thermal conductivity, thermal expansivity and heat capacities, as well as electronic and radiative thermal conductivities, have been derived for the mantles of super-Earths. These properties are necessary to understand the interior dynamics and the thermal evolution of those planets. We assume that the mantles consist of MgSiO₃ perovskite (pv), but we discuss the effects of the post-perovskite transition, and we elaborate on an addition of periclase MgO and incorporated Fe. However, MgO is found to only significantly influence the phonon thermal conductivity – the viscosities, heat capacities and thermal expansivities of pv and MgO remain comparable. We use the Keane theory of solids, which takes into account the behavior of solid matter at the infinite pressure limit, adopt the Keane equations of state, and adjust for pv and MgO by comparison with experimental high-pressure and high-temperature data. We find the theory of the infinite pressure limit of Keane to be in excellent agreement with recent ab initio studies and experiments. To calculate the melting curve, we further use the Lindemann–Stacey scaling law and fit it to available experimental data. The best data fitting melting temperature for pv reaches 5700 K at 135 GPa and increases to 20,000 K at 1.1 TPa, corresponding to the core-mantle boundary of a 10 Earth mass super-Earth (10M_Earth). We find the pv adiabatic temperature (with a potential temperature of 1700 K) to reach 2570 K at 135 GPa and 5000 K at 1.1 TPa. To calculate the pressure-and temperature-dependent viscosity, we use the semi-empirical homologous temperature scaling to relate enthalpy change, and hence viscosity, to the melting temperature. We find that the resulting activation volume of pv decreases from 2.8 cm³/mol at 25 GPa to 1.4 cm³/mol at 1.1 TPa-resulting in a viscosity increase by ～15 orders of magnitude through the adiabatic mantle of a 10M_Earth planet. Furthermore, the thermal expansivity (of pv and MgO) decreases by a factor of eight, and the total thermal conductivity (phonon, radiative and electronic) of an Earth-like pv/MgO composite increases by a factor of seven through an adiabatic mantle of a 10M_Earth super-Earth. At higher temperatures, i.e., for super-adiabatic temperature profiles, the electronic and radiative thermal conductivities strongly increase and dominate the conductive heat transport. All findings indicate an increase of heat transfer solely by conduction in the lower mantles of super-Earths. Thus our results disagree with Earth-biased full-mantle convection assumptions made by previous models for super-Earths, and additionally raise questions about the differentiation of massive rocky exoplanets and their ability to generate magnetic fields or sustain plate tectonics.     

Resistive tearing mode in coronal neutral sheets

The apparent stability of coronal neutral sheets with respect to the resistive tearing mode has been attributed by previous authors to the influence of a weak normal component of the confining magnetic field. To check this hypothesis a normal mode analysis is performed applying rigorously singular perturbation technique. Allowance is made for a value of the normal component which is large measured in the appropriate units deduced from the dynamics of the one-dimensional tearing mode. The structure of the eigenmodes is completely changed: the singular layer decays into a broad band of filaments with antiparallel flow directions and spatial oscillations in the perturbed current density appear. Surprisingly, the growth rate is not changed. If parameters for a typical neutral sheet in the middle corona (0.5 solar radii) are inserted, the result is that no stabilization by a normal component occurs, if the value of the growth time predicted by the one-dimensional theory is far shorter than ten minutes - independent of the values assumed for the width of the neutral sheet or the resistivity.