Acid-base properties of a goethite surface model: A theoretical view

Density functional theory is used to compute the effect of protonation, deprotonation, and dehydroxylation of different reactive sites of a goethite surface modeled as a cluster containing six iron atoms constructed from a slab model of the (1 1 0) goethite surface. Solvent effects were treated at two different levels: (i) by inclusion of up to six water molecules explicitly into the quantum chemical calculation and (ii) by using additionally a continuum solvation model for the long-range interactions. Systematic studies were made in order to test the limit of the fully hydrated cluster surfaces by a monomolecular water layer. The main finding is that from the three different types of surface hydroxyl groups (hydroxo, μ-hydroxo, and μ₃-hydroxo), the hydroxo group is most active for protonation whereas μ- and μ₃-hydroxo sites undergo deprotonation more easily. Proton affinity constants (pK_a values) were computed from appropriate protonation/deprotonation reactions for all sites investigated and compared to results obtained from the multisite complexation model (MUSIC). The approach used was validated for the consecutive deprotonation reactions of the [Fe(H₂O)₆]³⁺ complex in solution and good agreement between calculated and experimental pK_a values was found. The computed pK_a for all sites of the modeled goethite surface were used in the prediction of the pristine point of zero charge, pH_PPZN. The obtained value of 9.1 fits well with published experimental values of 7.0-9.5.     

Evaluation of thermal equations of state for CO2 in numerical simulations

Three commonly used thermal equations of state for carbon dioxide, as well as the ideal gas law, have been compared against a large number of measurement data taken from the literature. Complex equations of state reach a higher accuracy than simple ones. The inaccuracy of the density function can cause large errors in fluid property correlations, such as heat capacity or viscosity. The influence of this inaccuracy on the results of numerical simulations have been evaluated by two examples: The first one assumes isothermal gas expansion from a volume, while the second one considers heat transport along a fracture. For both examples, different equations of state have been utilized. The simulations have been performed on the scientific software platform OpenGeoSys. The difference among the particular simulation results is significant. Apparently small errors in the density function can cause considerably different results of otherwise identical simulation setups.     

以树轮宽度重建公元1558年以来华山5～6月平均温度及20世纪中后期升温

通过对秦岭东端华山地区油松树木年轮宽度序列的分析研究,探讨了华山地区油松对气候环境响应的敏感性,结果表明在华山地区油松对气温和降水的响应均高于华山松,与 5～6月平均温度相关较高,且通过了0.01显著性信度检验。在此基础上,我们重建了华山地区 1558～2006年间 5～6月的平均温度,重建序列的方差解释量达到41%。结果显示： 华山过去449年中,大部分年份 5～6月平均温度在平均值附近波动,变幅不大; 重建序列可与秦岭南五台 5～7月温度序列进行良好对比,其年际间相关系数达到了0.49(N＝246, p<0.0001)。华山地区20世纪 20～30年代初的暖期略偏低; 20世纪30年代中期至50年代是整个重建时段中低温持续时间较长的时段; 20世纪60年代之后,气温波动平缓; 从20世纪70年代开始快速升温,对全球变暖有较强响应。     

Superstructures in ankerite and calcite

Two rhombohedral carbonates, ferroan dolomite (ankerite) and magnesian calcite from lower Jurassic ammonites, have been studied by transmission electron microscopy. The samples show small domains with the morphology of platelets parallel to (11 \(\bar 2\) 0) which have exceptionally well ordered superstructures and characteristic c-reflections. Diffraction patterns and contrast analysis of atomic resolution images indicate that the domains observed in ankerite are rich in Ca [Ca_0.75(Mg, Fe)_0.25CO₃] and those in calcite rich in Mg, and there is strong evidence that cation ordering is the cause for the observed superstructures which are proposed mainly on diffraction evidence. Rhombohedral carbonates have a close similarity to NaCl, with CO₃-groups substituting for Cl. Cation ordering patterns can therefore be discussed in analogy to f.c.c. alloys. We make use of ordering waves to describe superstructures and to qualitatively interpret kinetic conditions for their formation.     

The geochemical composition of the terrestrial surface (without soils) and comparison with the upper continental crust

The terrestrial surface, the “skin of the earth”, is an important interface for global (geochemical) material fluxes between major reservoirs of the Earth system: continental and oceanic crust, ocean and atmosphere. Because of a lack in knowledge of the geochemical composition of the terrestrial surface, it is not well understood how the geochemical evolution of the Earth’s crust is impacted by its properties. Therefore, here a first estimate of the geochemical composition of the terrestrial surface is provided, which can be used for further analysis. The geochemical average compositions of distinct lithological classes are calculated based on a literature review and applied to a global lithological map. Comparison with the bulk composition of the upper continental crust shows that the geochemical composition of the terrestrial surface (below the soil horizons) is significantly different from the assumed average of the upper continental crust. Specifically, the elements Ca, S, C, Cl and Mg are enriched at the terrestrial surface, while Na is depleted (and probably K). Analysis of these results provide further evidence that chemical weathering, chemical alteration of minerals in marine settings, biogeochemical processes (e.g. sulphate reduction in sediments and biomineralization) and evaporite deposition are important for the geochemical composition of the terrestrial surface on geological time scales. The movement of significant amounts of carbonate to the terrestrial surface is identified as the major process for observed Ca-differences. Because abrupt and significant changes of the carbonate abundance on the terrestrial surface are likely influencing CO₂-consumption rates by chemical weathering on geological time scales and thus the carbon cycle, refined, spatially resolved analysis is suggested. This should include the recognition of the geochemical composition of the shelf areas, now being below sea level.     

Determination of major and trace elements in European bottled mineral water — Analytical methods

A total of 1785 European bottled water samples were analyzed using standard laboratory methods. The bottled water samples were purchased in 2008 at supermarkets throughout 40 European countries. The samples were analyzed for 71 chemical parameters (As, Al, As, B, Ba, Be, Bi, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge, Hf, Hg, Ho, I, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Nd, Ni, Pb, Pr, Rb, Sb, Sc, Se, Sm, Sn, Sr, Ta, Tb, Te, Th, Ti, Tl, Tm, U, V, W, Y, Yb, Zn, Zr, Br⁻, HCO₃⁻, Cl⁻, F⁻, NH₄⁺, NO₂⁻, NO₃⁻, PO₄³⁻, SO₄²⁻, SiO₂, pH, and EC) by quadrupole inductively coupled emission spectroscopy (ICP-QMS, trace elements), inductively coupled plasma atomic emission spectroscopy (ICP-AES, major elements), ion chromatography (IC, anions), atomic fluorescence spectrometry (AFS, Hg), titration (alkalinity), photometric methods (NH₄⁺), potentiometric methods (pH), and conductometric methods (specific electrical conductivity, EC). A very strict quality control procedure was followed by analysing blanks, international reference materials, an internal project standard, and duplicate analyses, as well as by analysing 23 elements by both ICP-QMS and ICP-AES. Analysis of marketed bottled water from springs, wells or boreholes, apart from the evaluation of its quality with respect to inorganic elements, it may provide a cheap alternative to obtain a first impression about groundwater chemistry at the European scale.     

Exceptional preservation of embryos in the actinopterygian Saurichthys from the Middle Triassic of Monte San Giorgio, Switzerland

New excavations in the famous Monte San Giorgio area, close to the historical sites where the Cassina beds crop out (Lower Meride Limestone, Early Ladinian), revealed an interesting vertebrate fauna, including several specimens of the actinopterygian fish Saurichthys. Among the prepared specimens, three specimens of Saurichthys contain embryos, and in one example the embryos are preserved with traces of the soft parts, most probably phosphatized musculature. This discovery is of particular relevance because fossil embryos with preserved soft parts are extremely rare. In addition, although viviparity had previously been described for Saurichthys, the new specimens are rather better evidence and add further support to this reproductive mode.     

Electron microscopy study of hyalomylonites—evidence for frictional melting in landslides

Hyalomylonites, from Langtang (Nepal) and Köfels (Ötz Valley, Austria), were investigated by transmission electron microscopy (TEM). The matrix is glassy at both localities; rarely it is crystallized and devitrified to dendrites and skeletal microlites of plagioclase, alkali feldspar and biotite. The matrix is chemically heterogeneous with schlieren and formed by partial to almost complete melting of host rocks of granitic to granodioritic composition. Locally, glasses with pure quartz, plagioclase and alkalifeldspar composition were found. From SiO₂-glass minimum temperatures of 1520°C are estimated.At both hyalomylonite localities melting appears to be the result of frictional heating on the gliding plane of a large landslide. The host rocks were deformed in a brittle mode. Microstructures typical of plastic deformation at high temperatures are displayed by inclusions and were probably inherited from previous tectonic events.     

Measurement of ocean temperature and salinity via microwave radiometry

Sea-surface temperature with an accuracy of 1 °C and salinity with an accuracy of 1 were measured with a 1.43 and 2.65 GHz radiometer system after correcting for the influence of cosmic radiation, intervening atmosphere, sea-surface roughness, and antenna beamwidth. The radiometers are a third-generation system using null-balancing and feed-back noise injection. Flight measurements from aircraft over bay regions and coastal areas of the Atlantic resulted in contour maps with spatial resolution of 0.5 km.