Experimental and theoretical bond critical point properties for model electron density distributions for earth materials

Generalized X-ray scattering factor model experimental electron density distributions and bond critical point, bcp, properties generated in recent studies for the earth materials stishovite, forsterite, fayalite and cuprite with high energy single crystal synchrotron X-ray diffraction data and those generated with high resolution diffraction data for coesite and senarmonite were found to be adequate and in relatively good agreement, ~5% on average, with those calculated with quantum chemical methods with relatively robust basis sets. High resolution low energy single crystal diffraction data, recorded for the molecular sieve AlPO₄-15, were also found to yield model electron density distribution values at the bcp points for the AlO and PO bonded interactions that are in relatively good to moderately good agreement with the theoretical values, but the Laplacian values of the distribution at the points for the two bonded interactions were found to be in relatively poor agreement. In several cases, experimental bcp properties, generated with conventional low energy X-ray diffraction data for several rock forming minerals, were found overall to be in poorer agreement with the theoretical properties. The overall agreement between theoretical bcp properties generated with computational quantum methods and experimental properties generated with synchrotron high energy radiation not only provides a basis for using computational strategies for studying and modeling structures and their electron density distributions, but it also provides a basis for improving our understanding of the crystal chemistry and bonded interactions for earth materials. Theoretical bond critical point properties generated with computational quantum methods are believed to rival the accuracy of those determined experimentally. As such the calculations provide a powerful and efficient method for evaluating electron density distributions and the bonded interactions for a wide range of earth materials.Dedicated to Professor Robert F. Stewart of Carnegie Mellon University on his retirement for his brilliant and original work modeling electron density distributions.     

Dating ultra-deep mine waters with noble gases and Cl, Witwatersrand Basin, South Africa

Concentrations and isotopic ratios of dissolved noble gases, ³⁶Cl, δD and δ¹⁸O in water samples from the ultra-deep gold mines (0.718 to 3.3 km below the surface) in the Witwatersrand Basin, South Africa, were investigated to quantify the dynamics of these ultra deep crustal fluids. The mining activity has a significant impact on the concentrations of dissolved gases, as the associated pressure release causes the degassing of the fissure water. The observed under saturation of the atmospheric noble gases in the fissure water samples (70-98%, normalized to ASW at 20°C and 1013 mbar) is reproduced by a model that considers diffusive degassing and solubility equilibration with a gas phase at sampling temperature. Corrections for degassing result in ⁴He concentrations as high as 1.55 · 10⁻¹cm³STP⁴He g⁻¹, ⁴⁰Ar/³⁶Ar ranging between 806 and 10331, and ¹³⁴Xe/¹³²Xe and ¹³⁶Xe/¹³²Xe ratios above 0.46 and 0.44, respectively. Corrected ^134(136)Xe/¹³²Xe and ^134(136)Xe/⁴He-ratios are consistent with their production ratios, whereas the nucleogenic ⁴He/⁴⁰Ar, and ^134(136)Xe/⁴⁰Ar ratios generally indicate that these gases are produced in an environment with an average [U + Th]/K-content 2-3 times above that of crustal average. In two scenarios, one considering only accumulation of in situ produced noble gases, the other additionally crustal flux components, the model ages for 14 individual water samples range from 13 to 168 Ma and from 1 to 23 Ma, respectively.The low ³⁶Cl-ratios of (4-37) · 10⁻¹⁵ and comparatively high ³⁶Cl-concentrations of (8-350) · 10⁻¹⁵ atoms ³⁶Cl l⁻¹ reflect subsurface production in secular equilibrium indicating an age in excess of 1.5 Ma or 5 times the half-life of ³⁶Cl.In combination, the results suggest residence times of the fluids in fissures in this region (up to 3.3 km depth) are of the order of 1-100 Ma. We cannot exclude the possibility of mixing and that small quantities of younger water have been mixed with the very old bulk.     

Solute transport in formations of very low permeability: profiles of stable isotope and dissolved noble gas contents of pore water in the Opalinus Clay, Mont Terri, Switzerland

Pore water profiles of water, stable isotope, and dissolved noble gas content have been determined across the Opalinus Clay and adjacent formations at the rock laboratory at Mont Terri. We have found enhanced helium contents (up to [⁴He] = 1 × 10⁻⁴ cubic centimeters at standard pressure and temperature per gram of pore water) and argon isotope ratios (⁴⁰Ar/³⁶Ar ratios up to 334) due to accumulation of ⁴He and ⁴⁰Ar produced in situ. The helium profile was found to be in steady state with respect to in situ production and diffusive loss into the adjacent limestones where groundwater circulates. From this profile a representative mean value of the apparent diffusion coefficient for helium in the pore water of the whole formation was derived for the first time to be D_a = 3.5 × 10⁻¹¹ m² · s⁻¹, which is more than two orders of magnitude lower than the diffusion coefficient D₀ in free water. The stable isotope profile, however, indicates a component of fossil marine pore water, which has not yet been replaced by molecular diffusion of meteoric water from the adjacent limestone and shale formations over the past 10 million years.     

Electron density distribution and bond critical point properties for forsterite, Mg2 SiO4, determined with synchrotron single crystal X-ray diffraction data

A generalized X-ray scattering factor model experimental electron density distribution has been generated for the orthosilicate forsterite, using an essentially extinction and absorption free set of single crystal diffraction data recorded with intense, high energy synchrotron X-ray radiation (E=100.6 keV). A refinement of the model converged with an R(F)=0.0061. An evaluation of the bond critical point, bcp, properties of the distribution at the (3, –1) stationary points for the SiO and MgO bonded interactions, yielded values that agree typically within ~5%, on average, with theoretical values generated with quantum chemical computational strategies, using relatively robust basis sets. On the basis of this result, the modeling of the experimental distribution is considered to be adequate. As the bcp properties increase in magnitude, the MgO and SiO bonds decrease in length as calculated for a number of rock forming silicates. As asserted by Coppens (X-ray charge densities and chemical bonding. Oxford University Press, Oxford, 1997), large negative ²(r_c) values, characteristic of shared interactions involving first row atoms, may not be characteristic of closed shell covalent bonded interactions involving second row Si, P and S atoms bonded to O. This study adds new evidence to the overall relatively good agreement between theoretical bcp properties generated with computational quantum strategies, on the one hand, and experimental properties generated with single crystal high energy synchrotron diffraction data on the other. The similarity of results not only provides a basis for using computational strategies for studying and modeling structures, defects and the reactivity of representative structures, but it also provides a basis for improving our understanding of the crystal chemistry of earth materials and the character of the SiO bonded interaction.     

Practical use of video imagery in nearshore oceanographic fieldstudies

An approach was developed for using video imagery to quantify, in terms of both spatial and temporal dimensions, a number of naturally occurring (nearshore) physical processes. The complete method is presented, including the derivation of the geometrical relationships relating image and ground coordinates, principles to be considered when working with video imagery and the two-step strategy for calibration of the camera model. The techniques are founded on the principles of photogrammetry, account for difficulties inherent in the use of video signals, and have been adapted to allow for flexibility of use in field studies. Examples from field experiments indicate that this approach is both accurate and applicable under the conditions typically experienced when sampling in coastal regions. Several applications of the camera model are discussed, including the measurement of nearshore fluid processes, sand bar length scales, foreshore topography, and drifter motions. Although we have applied this method to the measurement of nearshore processes and morphologic features, these same techniques are transferable to studies in other geophysical settings     

Enhancement of (0k0) reflections of clay minerals in a Guinier camera

In oriented aggregates of flake-like clay minerals the (0k0) planes tend to orient in such a way that their normals become aligned subparallel to the specimen layer. This property may be utilized to obtain enhanced (060) intensities provided that the normal of the clay layer and the primary beam intersect at an angle equal to the Bragg angle for (060). This condition may be satisfied in a Guinier camera.From the degree of orientation t(_00l) of the basal planes the enhancement factor t _(0k0) is calculated according to three models. For t _(00l) between 5 and 50 times the intensity of random orientation the enhancement t _(0k0) varies between 2 and 5.5 times.     

Die Kristallstruktur des Norsethit,BaMg(CO3)2

Zusammenfassung Künstlicher Norsethit, BaMg(CO₃)₂, hat die hexagonalen Gitterkonstanten:a=5,017±0,001 Å undc=16,77±0,01 Å; Z=3. Die Struktur wurde auf Grund von 30 unabhängigen Röntgenpulverreflexen bestimmt. Sie wird in der Raumgruppe R32 mit R=0,035 durch die Sauerstoffparameter (hexagonal): x=0,199; y=–0,089 und z=0,242 beschrieben. Die übrigen Atome haben analoge Lagen wie im Dolomit. Das Magnesium ist verzerrt oktaedrisch durch Sauerstoff umgeben. Das Barium ist in Form eines trapezoedrisch verzerrten ditrigonalen Prismas durch 12 Sauerstoffatome koordiniert. Die wichtigsten Abstände sind: Mg–O=2,09₃Å (6X); Ba–O (kurz) =2,71₅Å (6X) und Ba–O (lang)=3,18₄Å (6X).

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Summary Artificial norsethite, BaMg(CO₃)₂ has the hexagonal lattice constants:a=5,017±0,001 Å andc=16.77±0.01 Å; Z=3. The structure was determined on the basis of 30 independent X-ray powder reflections. In the space group R32 it is described with R=0.035 by the following oxygene parameters (hex.):x=0.199;y=–0.089 andz=0.242. The other atoms occupy analogous positions as in dolomite. Magnesium has a distorted octahedral coordination by oxygene. Barium is surrounded by 12 oxygenes at the corners of a trapezohedrally distorted ditrigonal prism. Important bond lengths are Mg–O=2.09₃Å (6X); Ba–O (short)=2.71₅Å (6X) and Ba–O (long)=3.18₄Å (6X).

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Mit 4 Textabbildungen     

Die Petrographie des Knollenmergel,Mittlerer Keuper,Trias

In Württemberg, the upper part of the Middle Keuper is referred to as “Knollenmergel” (= “nodular marl”, a marly claystone containing carbonate nodules), 24 samples were studied from a test well located near Hechingen. X-ray diffraction was used for the determination of the mineral composition of whole rocks and of the clay fractions. The coarser fractions were studied under the petrographic microscope. The fractions < 2π Ø consist chiefly of an mixed-layer mineral with illite and expandable, montmorillonite-like layers as the components. There are about 30 % of expandable layers. A low-angle reflection near 31 Å is indicative of considerable order among component-layer species approaching that of rectorite. In the lower part of the section, moderate amounts of sudoite are present in addition. Illite as a discrete phase could not be determined with certainty. The microscopic fractions consist partly of monomineralic grains of quarz, dolomite, and calcite. In addition, they contain considerable amounts of polymineralic aggregates, which were not dispersed by the rather mild disintegration method used in the present study. Accordingly, the rocks are claystones characterized by the same degree of lithification as those occurring in other parts of the Keuper in Württemberg. The interstratified mineral is tentatively derived from the erosion of a uniform body of volcanogenic material of Paleozoic age. On the basis of grain-size distribution, the Knollenmergel is a water-laid sediment. Eolian transport as advocated by some geologists can be excluded. The difficulties experienced with the Knollenmergel as a building ground are explained by the high percentage of the expandable interstratified mineral and the dearth of a genuine sand fraction.     

Siphonostomatoid copepods infecting Squalus acutipinnis Regan, 1908 off South Africa

Squalus acutipinnis (previously included in S. megalops) individuals caught off the east, south and west coasts of South Africa were examined for siphonostomatoid copepod infection. Collected siphonostomatoids were fixed and preserved in 70% ethanol and studied under microscopes using both transmitted and incidental light. The copepods were identified and the host-parasite associations estimated by calculating their prevalence, mean intensity and mean abundance. The siphonostomatoids represented four families and six species, and included new host records for Nemesis sp., Lernaeopoda sp. and Eudactylina acanthii, and a new geographical record for E. acanthii. Squalus acutipinnis individuals were infected by relatively low loads of siphonostomatoids. The most commonly found species was Achtheinus pinguis, the only species found off all three coasts. There was no difference in the prevalence of A. pinguis in sharks sampled off the three coasts but the highest mean intensity was found on the East Coast followed by the West Coast. The overall prevalence of A. pinguis was 33.6%, and was an order of magnitude higher than that of the other siphonostomatoids recorded. At such low levels of infection it will thus be necessary to examine a large number of hosts to determine the biodiversity of siphonostomatoids and geographical differences in prevalence in South African waters.