Volume diffusion of Ytterbium in YAG: thin-film experiments and combined TEM–RBS analysis

In this study, we address volume diffusion of ytterbium in yttrium aluminum garnet (YAG) using thin-film single crystal diffusion couples. We employ analytical transmission electron microscopy (ATEM) as a tool for combined microstructural and microchemical analysis and compare the results to Rutherford backscattering (RBS) analysis. Given the high spatial resolution of the method, we focus on microstructural changes of the thin-film diffusant source during the diffusion anneal. We evaluate the potential influence of the associated changes in its transport properties on the evolution of concentration profiles in the single crystal substrate. This approach allows us to test the reliability of determination of volume diffusion coefficients from thin-film diffusion experiments. We found that for the chosen experimental setting, the influence of thin-film re-crystallization is small when compared with the experimental uncertainty and good estimates for the volume diffusion coefficients of Yb in YAG can be obtained using standard assumptions. Both Yb-concentration profiles analyzed with ATEM and with RBS give similar results. At 1,450°C and 1 bar, we infer log D _Yb (m²/s) values of −19.37 ± 0.07 (TEM) and −19.84 ± 0.02 (RBS). Although the change in thin-film transport properties associated with successive crystallization during the diffusion anneal does not play a major role for our experimental setup, this effect cannot generally be ignored.     

Sulfur in presolar silicon carbide grains from asymptotic giant branch stars

We studied 14 presolar SiC mainstream grains for C‐, Si‐, and S‐isotopic compositions and S elemental abundances. Ten grains have low levels of S contamination and CI chondrite‐normalized S/Si ratios between 2 × 10^?5 and 2 × 10^?4. All grains have S‐isotopic compositions compatible within 2σ of solar values. Their mean S isotope composition deviates from solar by at most a few percent, and is consistent with values observed for the carbon star IRC+10216, believed to be a representative source star of the grains, and the interstellar medium. The isotopic data are also consistent with stellar model predictions of low‐mass asymptotic giant branch (AGB) stars. In a δ³³S versus δ³⁴S plot the data fit along a line with a slope of 1.8 ± 0.7, suggesting imprints from galactic chemical evolution. The observed S abundances are lower than expected from equilibrium condensation of CaS in solid solution with SiC under pressure and temperature conditions inferred from the abundances of more refractory elements in SiC. Calcium to S abundance ratios are generally above unity, contrary to expectations for stoichiometric CaS solution in the grains, possibly due to condensation of CaC₂ into SiC. We observed a correlation between Mg and S abundances suggesting solid solution of MgS in SiC. The low abundances of S in mainstream grains support the view that the significantly higher abundances of excess ³²S found in some Type AB SiC grains are the result of in situ decay of radioactive ³²Si from born‐again AGB stars that condensed into AB grains.     

Development and Re‐Evaluation of Tourmaline Reference Materials for In Situ Measurement of Boron δ Values by Secondary Ion Mass Spectrometry

Six tourmaline samples were investigated as potential reference materials (RMs) for boron isotope measurement by secondary ion mass spectrometry (SIMS). The tourmaline samples are chemically homogeneous and cover a compositional range of tourmaline supergroup minerals (primarily Fe, Mg and Li end‐members). Additionally, they have homogeneous boron delta values with intermediate precision values during SIMS analyses of less than 0.6‰ (2s). These samples were compared with four established tourmaline RMs, that is, schorl IAEA‐B‐4 and three Harvard tourmalines (schorl HS#112566, dravite HS#108796 and elbaite HS#98144). They were re‐evaluated for their major element and boron delta values using the same measurement procedure as the new tourmaline samples investigated. A discrepancy of about 1.5‰ in δ¹¹B was found between the previously published reference values for established RMs and the values determined in this study. Significant instrumental mass fractionation (IMF) of up to 8‰ in δ¹¹B was observed for schorl–dravite–elbaite solid solutions during SIMS analysis. Using the new reference values determined in this study, the IMF of the ten tourmaline samples can be modelled by a linear combination of the chemical parameters FeO + MnO, SiO₂ and F. The new tourmaline RMs, together with the four established RMs, extend the boron isotope analysis of tourmaline towards the Mg‐ and Al‐rich compositional range. Consequently, the in situ boron isotope ratio of many natural tourmalines can now be determined with an uncertainty of less than 0.8‰ (2s).     

Simulation of DNAPL infiltration and spreading behaviour in the saturated zone at varying flow velocities and alternating subsurface geometries

The influence of varying groundwater flow velocities on DNAPL infiltration and spreading behaviour was investigated by multiphase modelling using TMVOC and PetraSim. The multiphase models were calibrated by results of previously conducted laboratory experiments for the complete spatio-temporal range of the experiments. The small scale 2D scenario modelling was applied to qualify and quantify changes in position, architecture, geometry and dissolution of a TCE body in a fully saturated homogeneous sandy medium. The applied flow velocities ranging from 0.05 up to 40.00 m/day exhibited that the DNAPL TCE is affected even at the lowest flow velocity in its position, its size and its architecture. Additionally, several impermeable lenses with simple geometry were assumed in the model, to investigate the influence of stratified subsoil. In the experimental set-ups, the DNAPL body reacts more sensitive to the applied groundwater flow velocities than to the geometrical set-up of the scenarios. A possible consequence can be the transportation and displacement of a DNAPL pool due to natural or anthropogenic induced high groundwater flow velocities, as by Pump and Treat facilities, complicating site investigation process and planning of remediation activities.     

Perception of landslides risk and responsibility: a case study in eastern Styria, Austria

This paper presents a case study about the perception of landslide risk. Following a major set of landslides in the eastern part of Austria in June 2009, we surveyed local experts, residents who had suffered losses from the landslides, and others living in the affected communities. Overall, the risk perception was significantly higher among those who had been personally affected by a landslide, had knowledge of the geology in the study region, had been affected by another natural hazard, or spent a lot of time outdoors and in touch with nature. Non-experts viewed natural factors as the main causes for the occurrence of landslides, while experts viewed anthropogenic factors as more important. Likewise, non-experts placed a greater emphasis on hard measures (such as retaining walls) to reduce the risk, whereas the experts tended to focus on better information and land-use planning. In terms of responsibility for mitigative actions, a majority of inhabitants believed that public authorities should undertake most of the costs, whereby those who had personal experience with landslides were more likely to favor the government paying for it.     

Stress Sensitivity of Seismic and Electric Rock Properties of the Upper Continental Crust at the KTB

We test the hypothesis that the general trend of P-wave and S-wave sonic log velocities and resistivity with depth in the pilot hole of the KTB site Germany, can be explained by the progressive closure of the compliant porosity with increasingly effective pressure. We introduce a quantity θ_c characterizing the stress sensitivity of the mentioned properties. An analysis of the downhole measurements showed that estimates of the quantitiy θ_c for seismic velocities and electrical formation factor of the in situ formation coincide. Moreover, this quantity is 3.5 to 4.5 times larger than the averaged stress sensitivity obtained from core samples. We conclude that the hypothesis mentioned above is consistent with both data sets. Moreover, since θ_c corresponds approximately to the inverse of the effective crack aspect ratio, larger in situ estimates of θ_c might reflect the influence of fractures and faults on the stress sensitivity of the crystalline formation in contrast to the stress sensitivity of the nearly intact core samples. Finally, because the stress sensitivity is directly related to the elastic nonlinearity we conclude that the elastic nonlinearity (i.e., deviation from linear stress-strain relationship i.e., Hooke's law) of the KTB rocks is significantly larger in situ than in the laboratory.     

The most frequent interfaces in olivine aggregates: the GBCD and its importance for grain boundary related processes

Rocks consist of crystal grains separated by grain boundaries that impact the bulk rock properties. Recent studies on metals and ceramics showed that the grain boundary plane orientation is more significant for grain boundary properties than other characteristics such as the sigma value or disorientation (in the Earth’s science community more frequently termed misorientation). We determined the grain boundary character distribution (GBCD) of synthetic and natural polycrystalline olivine, the most abundant mineral of Earth’s upper mantle. We show that grain boundaries of olivine preferentially contain low index planes, in agreement with recent findings on other oxides (e.g. MgO, TiO₂, Al₂O₃ etc.). Furthermore, we find evidence for a preferred orientation relationship of 90° disorientations about the [001] direction forming tilt and twist grain boundaries, as well as a preference for the 60° disorientation about the [100] axis. Our data indicate that the GBCD, which is an intrinsic property of any mineral aggregate, is fundamental for understanding and predicting grain boundary related processes.     

Seasonality change and the third millennium BP rainforest crisis in southern Cameroon (Central Africa)

The third millennium BP crisis of the central African rainforest is not sufficiently understood. The low resolution of most pollen profiles and a large plateau of the calibration curve aggravate the exact dating of the event, and its causal climatic parameters are debated. We present a high-resolution pollen profile from the swamp site Nyabessan in the southern Cameroonian rainforest, covering the period 3100-2300 cal yr BP. Between 3100 and 2500 cal yr BP, the climate was favourable for a regional evergreen forest with Caesalpiniaceae and Lophira and a local Raphia swamp forest. Around 2500/2400 cal yr BP, a significant decrease of mature forest and swamp forest taxa and an increase of pioneers indicate that the rain forest was seriously disturbed and replaced by secondary formations. The dominance of Trema orientalis, a pioneer well adapted to seasonal desiccation, points to a much more accentuated seasonality after 2500 cal yr BP, which seems to be linked to a southwards shift of the ITCZ during the northern hemisphere winter months. We propose that the rain forest crisis between 2500 and 2200 cal BP created favourable conditions for farming and paved the way for a major expansion of Bantu speaking populations.     

Stable carbon isotope distribution of particulate organic matter in the ocean: a model study

The stable carbon isotopic composition of particulate organic matter in the ocean, δ¹³C_POC, shows characteristic spatial variations with high values in low latitudes and low values in high latitudes. The lowest δ¹³C_POC values (−32‰ to −35‰) have been reported in the Southern Ocean, whereas in arctic and subarctic regions δ¹³C_POC values do not drop below −27‰. This interhemispheric asymmetry is still unexplained. Global gradients in δ¹³C_POC are much greater than in δ¹³C_DIC, suggesting that variations in isotopic fractionation during organic matter production are primarily responsible for the observed range in δ¹³C_POC. Understanding the factors that control isotope variability is a prerequisite when applying δ¹³C_POC to the study of marine carbon biogeochemistry. The present model study attempts to reproduce the δ¹³C_POC distribution pattern in the ocean. The three-dimensional (3D) Hamburg Model of the Oceanic Carbon Cycle version 3.1 (HAMOCC3.1) was combined with two different parametrizations of the biological fractionation of stable carbon isotopes. In the first parametrization, it is assumed that the isotopic fractionation between CO₂ in seawater and the organic material produced by algae, _P, is a function of the ambient CO₂ concentration. The two parameters of this function are derived from observations and are not based on an assumption of any specific mechanism. Thus, this parametrization is purely empirical. The second parametrization is based on fractionation models for microalgae. It is supported by several laboratory experiments. Here the fractionation, _P, depends on the CO₂ concentration in seawater and on the (instantaneous) growth rates, μ_i, of the phytoplankton. In the Atlantic Ocean, where most field data are available, both parametrizations reproduce the latitudinal variability of the mean δ¹³C_POC distribution. The interhemispheric asymmetry of δ¹³C_POC can mostly be attributed to the interhemispheric asymmetry of CO₂ concentration in the water. However, the strong seasonal variations of δ¹³C_POC as reported by several authors, can only be explained by a growth rate-dependent fractionation, which reflects variations in the cellular carbon demand.     

Gradients in coral reef communities exposed to muddy river discharge in Pohnpei,Micronesia

This study analyzed how coral communities change along a gradient of increasing exposure to a mud-discharging river in the Enipein Catchment, Pohnpei, Micronesia. Using video transects, we quantified benthic communities at five sites along a gradient moving away from the river mouth towards the barrier reef. The most river-impacted site was characterized by a high accumulation of mud, low coral cover and low coral diversity. Although coral cover leveled off at ∼400 m from the river mouth to values found at the outer-most sites, coral diversity continued to increase with increasing distance, suggesting that the most distant site was still impacted by the river discharges. Fungiidae, Pavona, Acropora, Pachyseris and Porites rus all significantly increased in cover with distance from the river, while Turbinaria decreased. The combined presence and abundance of these six species groups, together with coral species richness, may help to indicate the effects of terrestrial runoff in similar runoff-exposed settings around Micronesia, whereas coral cover is not a sensitive indicator for river impact. Coral reefs are important resources for the people of Pohnpei. To prevent further degradation of this important resource, an integrated watershed approach is needed to control terrestrial activities.