The Bayesian approach to an internally consistent thermodynamic database: theory, database, and generation of phase diagrams

An internally consistent thermodynamic dataset has been derived for 148 endmember phases (145 solids and 3 fluids) comprising the elements Li, Na, K, Be, Mg, Ca, Ti, Cr, Mn, Fe, Zn, Al, Si, C, H, and O. This has been achieved by simultaneous treatment of phase property (like standard enthalpy of formation, standard entropy, molar heat capacity, molar volume, thermal expansivity, bulk modulus etc.) and reaction reversal data by the Bayesian method. The theory underlying the approach, and the computational methods involved, are briefly outlined. (For the benefit of readers unfamiliar with inference statistics, the basic concepts of the Bayes method are also presented in such a way that they can be grasped intuitively.) Although not yet addressed, this method can be extended to refine the thermodynamic mixing properties of crystalline solutions. The sources of the input data, culled from the literature, are summarized in the Appendix. The resulting database is succinctly documented in this paper. It includes the enthalpies of formation and entropies, their uncertainties, and the correlation among them. The database allows calculation of P-T, T-X _CO2, P-X _CO2, and T-f _O2 sections, with error propagation into the computed phase diagrams on a routine basis. A user-friendly computer program has been written to generate such phase diagrams. It is public domain software. The software and the thermodynamic database (which includes a complete documentation of the thermodynamic data above and beyond those listed (Table 2, here) may be downloaded from the web site http://homepage.ruhr-uni-bochum.de/niranjan.chatterjee/Index.htm. Examples of computed phase diagrams are given to illustrate the quality of the data and the capabilities of the software. Received: 11 March 1998 / Accepted: 11 June 1998     

Comparison of Galerkin-type discretization techniques for two-phase flow in heterogeneous porous media

A comparison of Standard Galerkin, Petrov-Galerkin, and Fully-Upwind Galerkin methods for the simulation of two-phase flow in heterogeneous porous media is presented. On the basis of the coupled pressure-saturation equations, a generalized formulation for all three finite element methods is derived and analysed. For flow in homogeneous media, the Petrov-Galerkin method gives excellent results. But this method fails miserably for problems with heterogeneous media. This is because it is not able to capture correctly processes that take place at interfaces when, for instance, the capillary pressure-saturation relationship after Brooks and Corey is assumed. The Fully-Upwind Galerkin method is superior to the Petrov-Galerkin approach because it is able to give correct results for flow in homogeneous and heterogeneous media for the two models of van Genuchten and Brooks-Corey. The widely used formulation which is correct for the homogeneous case cannot be used for heterogeneous media. Instead the straightforward approach of gradp_c in combination with a chord-slope technique must be utilized.     

The lower symmetric regime and its transition to waves in rotating annulus convection

Measurements of the temperature and zonal velocity fields which develop in a rotating annulus of fluid with an upper surface, differentially heated from the inner to outer cylinder, are described for the lower symmetric regime (small radial temperature differences). The temperature field is essentially conductive for moderate to large rotation rates, Ω (>1.0 sec⁻¹). The zonal velocity field is poorly approximated by the thermal wind equation.Measurements of the transition to waves from the lower symmetric regime at very large rotation rates are presented for positive and negative radial temperature differences. They suggest that the centrifugal buoyancy force and the free surface curvature may be important factors for the lower symmetric-wave transition at large Ω. By varying the stratification of the fluid over a range of 10³ independently of the radial temperature difference, Δr_wT, it is conclusively shown that several theories are correct in predicting that the lower symmetric transition is independent of the stratification at small Δr_wT > 0 for large enough Ω.     

Charcoal and fossil wood from palaeosols,sediments and artificial structures indicating Late Holocene woodland decline in southern Tibet (China)

Charcoal and fossil wood taken from palaeosols, sediments and artificial structures were analysed in order to evaluate the regional pedoanthracological potential and to obtain information on Holocene environmental changes, particularly on possible past tree occurrences in southern Tibet. This research was initiated by the question to what extent this area is influenced by past human impact. Even recent evaluations have perceived the present treeless desertic environment of southern Tibet as natural, and the previous Holocene palaeoenvironmental changes detected were predominantly interpreted to be climate-determined. The material analysed – comprising a total of 53 botanical spectra and 55 radiocarbon datings from 46 sampling sites (c. 3500–4700 m a.s.l.) – represents the largest systematically obtained data set of charcoal available from Tibet so far. 27 taxa were determined comprising trees, (dwarf-) shrubs and herbs as well as grasses. The predominant tree taxa were Juniperus, Hippophae, Salix and Betula. According to their present-day occurrence in the region, the genera Juniperus and Hippophae can be explicitly attributed to tree species. Further, less frequently detected tree taxa were Populus, Pinus, Quercus, Taxus and Pseudotsuga. Charcoal of Juniperus mainly occurred on southern exposures, whereas Betula was associated with northern exposures. In contrast, the (partly) phreatophytic taxa Hippophae and Salix showed no prevalent orientation. The distribution of radiocarbon ages on charcoal revealed a discontinuous record of burning events cumulating in the Late Holocene (c. 5700–0 cal BP). For southern Tibet, these results indicated a Late Holocene vegetation change from woodlands to the present desertic pastures. As agrarian economies in southern and south-eastern Tibet date back to c. 3700 and 5700 cal BP, respectively, and the present-day climate is suitable for tree growth up to c. 4600 m a.s.l., we concluded that the Late Holocene loss or thinning out of woodlands had been primarily caused by humans.     

Bounce Rock—A shergottite‐like basalt encountered at Meridiani Planum,Mars

Abstract– The Opportunity rover of the Mars Exploration Rover mission encountered an isolated rock fragment with textural, mineralogical, and chemical properties similar to basaltic shergottites. This finding was confirmed by all rover instruments, and a comprehensive study of these results is reported here. Spectra from the miniature thermal emission spectrometer and the Panoramic Camera reveal a pyroxene‐rich mineralogy, which is also evident in Mössbauer spectra and in normative mineralogy derived from bulk chemistry measured by the alpha particle X‐ray spectrometer. The correspondence of Bounce Rock’s chemical composition with the composition of certain basaltic shergottites, especially Elephant Moraine (EET) 79001 lithology B and Queen Alexandra Range (QUE) 94201, is very close, with only Cl, Fe, and Ti exhibiting deviations. Chemical analyses further demonstrate characteristics typical of Mars such as the Fe/Mn ratio and P concentrations. Possible shock features support the idea that Bounce Rock was ejected from an impact crater, most likely in the Meridiani Planum region. Bopolu crater, 19.3 km in diameter, located 75 km to the southwest could be the source crater. To date, no other rocks of this composition have been encountered by any of the rovers on Mars. The finding of Bounce Rock by the Opportunity rover provides further direct evidence for an origin of basaltic shergottite meteorites from Mars.     

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.     

A water movement study in Lianzhou Bay,Guangxi Province,China

This study investigates the physical conditions (water depth, current speed, salinity, temperature) in Lianzhou Bay, a shallow coastal bay in southern China, during two expeditions in the dry and wet seasons of 2011. Based on these expedition data, basic hydrodynamic parameters like Brunt-Väisälä Frequency, Richardson Number, Rossby radius, and Resonance Period are calculated. The results show that Lianzhou Bay is characterized by comparatively small quantity of freshwater input and weak stratification. Strong tides, which are spatially uniform within the bay, cause turbulent mixing. Residence time of the water is shorter in winter due to a stronger coastal current in that season. Consideration of the water movement may help to reduce the harmful ecological impact of aquaculture waste water discharge.     

A new pathway for Deep water exchange between the Natal Valley and Mozambique Basin?

Although global thermohaline circulation pathways are fairly well known, the same cannot be said for local circulation pathways. Within the southwest Indian Ocean specifically there is little consensus regarding the finer point of thermohaline circulation. We present recently collected multibeam bathymetry and PARASOUND data from the northern Natal Valley and Mozambique Ridge, southwest Indian Ocean. These data show the Ariel Graben, a prominent feature in this region, creates a deep saddle across the Mozambique Ridge at ca. 28°S connecting the northern Natal Valley with the Mozambique Basin. Results show a west to east change in bathymetric and echo character across the northern flank of the Ariel Graben. Whereby eroded plastered sediment drifts in the west give way to aggrading plastered sediment drift in the midgraben, terminating in a field of seafloor undulations in the east. In contrast, the southern flank of the Ariel Graben exhibits an overall rugged character with sediments ponding in bathymetric depressions in between rugged sub/outcrop. It is postulated that this change in sea-floor character is the manifestation of deep water flow through the Ariel Graben. Current flow stripping, due to increased curvature of the graben axis, results in preferential deposition of suspended load in an area of limited accommodation space consequently developing an over-steepened plastered drift. These deposited sediments overcome the necessary shear stresses, resulting in soft sediment deformation in the form of down-slope growth faulting (creep) and generation of undulating sea-floor morphology. Contrary to previous views, our works suggests that water flows from west to east across the Mozambique Ridge via the Ariel Graben.     

Simulated response to inter-annual SST variations in the Gulf Stream region

Recent studies show that mid-latitude SST variations over the Kuroshio-Oyashio Extension influence the atmospheric circulation. However, the impact of variations in SST in the Gulf Stream region on the atmosphere has been less studied. Understanding the atmospheric response to such variability can improve the climate predictability in the North Atlantic Sector. Here we use a relatively high resolution (～1°) Atmospheric General Circulation Model to investigate the mechanisms linking observed 5-year low-pass filtered SST variability in the Gulf Stream region and atmospheric variability, with focus on precipitation. Our results indicate that up to 70 % of local convective precipitation variability on these timescales can be explained by Gulf Stream SST variations. In this region, SST and convective precipitation are strongly correlated in both summer (r = 0.73) and winter (r = 0.55). A sensitivity experiment with a prescribed local warm SST anomaly in the Gulf Stream region confirms that local SST drives most of the precipitation variability over the Gulf Stream. Increased evaporation connected to the anomalous warm SST plays a crucial role in both seasons. In summer there is an enhanced local SLP minimum, a concentrated band of low level convergence, deep upward motion and enhanced precipitation. In winter we also get enhanced precipitation, but a direct connection to deep vertical upward motion is not found. Nearly all of the anomalous precipitation in winter is connected to passing atmospheric fronts. In summer the connection between precipitation and atmospheric fronts is weaker, but still important.     

DEM Simulation of Direct Shear: 1. Rupture Under Constant Normal Stress Boundary Conditions

A particle-based distinct element method and its grain-based method are used to generate and simulate a synthetic specimen calibrated to the rupture characteristics of an intact (non-jointed) low-porosity brittle rock deformed in direct shear. The simulations are compared to the laboratory-generated ruptures and used to investigate rupture at various normal stress magnitudes. The fracturing processes leading to shear rupture zone creation and the rupture mechanism are found to be normal stress dependent (progressing from tensile splitting to shear rupture) and show partial confirmation of rupture zone creation in nature and in experiments from other materials. The normal stress dependent change is found to be due to the orientation of the major principal stress and local stress concentrations internal to the synthetic specimens being deformed. The normal stress dependent rupture creation process results in a change to the rupture zone’s geometry, shear stress versus horizontal displacement response, and thus ultimate strength.