Polycyclic aromatic hydrocarbons (PAHs) in Antarctic Martian meteorites, carbonaceous chondrites, and polar ice

Recent analyses of the carbonate globules present in the Martian meteorite ALH84001 have detected polycyclic aromatic hydrocarbons (PAHs) at the ppm level (McKay et al., 1996). The distribution of PAHs observed in ALH84001 was interpreted as being inconsistent with a terrestrial origin and were claimed to be indigenous to the meteorite, perhaps derived from an ancient martian biota. We have examined PAHs in the Antarctic shergottite EETA79001, which is also considered to be from Mars, as well as several Antarctic carbonaceous chondrites. We have found that many of the same PAHs detected in the ALH84001 carbonate globules are present in Antarctic carbonaceous chondrites and in both the matrix and carbonate (druse) component of EETA79001. We also investigated PAHs in polar ice and found that carbonate is an effective scavenger of PAHs in ice meltwater. Moreover, the distribution of PAHs in the carbonate extract of Antarctic Allan Hills ice is remarkably similar to that found in both EETA79001 and ALH84001. The reported presence of L-amino acids of apparent terrestrial origin in the EETA79001 druse material (McDonald and Bada, 1995) suggests that this meteorite is contaminated with terrestrial organics probably derived from Antarctic ice meltwater that had percolated through the meteorite. Our data suggests that the PAHs observed in both ALH84001 and EETA79001 are derived from either the exogenous delivery of organics to Mars or extraterrestrial and terrestrial PAHs present in the ice meltwater or, more likely, from a mixture of these sources. It would appear that PAHs are not useful biomarkers in the search for extinct or extant life on Mars.     

Signatures of solar wind interaction with the nightside ionosphere of Venus

Plasma and field relationships observed across the nightside of Venus evidence a chaotic variety of interactions between the ionosphere and the combined effect of the solar wind and interplanetary magnetic field draped about the planet. Close examination of these data reveal within the chaos a number of repeatable signatures key to understanding fundamental field-plasma interactions. Observed from the Pioneer Venus Orbiter, (PVO), nightside conditions range from extensive, full-up ionospheres with little evidence of dynamic or energetic perturbations, to an almost full depletion, sometimes described as disappearing ionospheres. Between these extremes, the ionospheric structure is often irregular, sometimes exhibiting well-defined density troughs, at other times complex intervals of either abundant or minimal plasma concentration. Consistently, large B-fields (typically exceeding 5–10 nanoteslas) coincide with plasma decreases, whereas stable, abundant plasma distributions are associated with very low-level field. We examine hundreds of nightside orbits, identifying close correlations between regions of elevated magnetic fields featuring polarity reversals, and (a) exclusive low-frequency or distinctive broadband noise, or both, in the electric field data, (b) turbulent, superthermal behavior of the the ions and electrons. We review extensive studies of nightside fields to show that the correlations observed are consistent with theoretical arguments that the presence of strong magnetic fields within normal ionospheric heights indicates the intrusion of magnetosheath fields and plasma within such regions. We find abundant evidence that the ionosphere is frequently disrupted by such events, exhibiting a chaotic, auroral-like complexity appearing over a wide range of altitude and local time. We show that field-plasma disturbances, widely suggested to be similar to conditions in the Earth's auroral regions, are tightly linked to the electric field noise otherwise attributed to lightning. Owing to the coincidence inherent in this relationship, we suggest that natural, predictable plasma instabilities associated with the plasma gradients and current sheets evident within these events produce the E-field noise. The data relationships argue for a more detailed investigation of solar wind induced E-field noise mechanisms as the appropriate scientific procedure for invoking sources for the noise previously attributed to lightning. Consistent with these views, we note that independent analyses have offered alternative explanations of the noise as arising from ionospheric disturbances, that repeated searches for optical evidence of lightning have found no such evidence, and that no accepted theoretical work has yet surfaced to support the inference of lightning at Venus.     

Towards models of strategic spatial choice behaviour: theory and application issues

Models of spatial choice behaviour have been around in geography urban planning for decades to assess the feasibility of planning actions or to predict external (competition) effects on existing destinations. Although these models differ in terms of complexity and key concepts, they all have in common that spatial choice behaviour is predicted as a function of the attributes of the choice alternatives and distance or travel time separation only. None of these models do take into account that the attributes of choice alternatives and travel time may be highly non-stationary and that often the utility that people derive from visiting a particular location also depends on the choice behaviour of other individuals. Under these circumstances, individuals may exhibit strategic choice behaviour. That is, they will choose particular choice options taking into account their expected behaviour of others such as to maximize their own utility. The purpose of the proposed paper is to discuss possible models of strategic choice behaviour for these urban planning problems. Theory will be outlined and some critical issues in the application of such models to problems of spatial choice will be discussed.     

Constraints on the timing of granite emplacement, deformation and metamorphism in the Shamva area, Zimbabwe

In order to constrain the temporal relationship between granite (sensu lato) emplacement and metamorphism, isotope work was carried out on the minerals zircon and apatite (U-Pb), garnet (Pb-Pb) and hornblende (Ar-Ar) from wall rock samples in the Shamva area in Zimbabwe. The area, encompassing parts of the Chinamora and Murehwa batholiths and a wedge-shaped greenstone belt segment in between, is commonly quoted in the literature as an example illustrating pluton emplacement processes and deformational models for the Archean. New U-Pb dating of apatite from a boudinaged pegmatite within mafic schists in the batholith-greenstone contact zone has yielded an age of 2619 +28/-24 Ma. This age is interpreted as the best estimation of the intrusion age of this unit, depending on the assumed closure temperature, and provides an upper age limit for the syntectonic emplacement of the now gneissic granites. Pb-Pb dating of late kinematic garnets in cordierite-bearing rocks within the greenstone belt wall rocks gives an age of 2623NJ Ma. Together, this timing of relatively late, syntectonic plutonism and metamorphic mineral growth at ca. 2.62 Ga compares well with existing zircon crystallization ages for felsic volcanics (2645dž Ma, 2643NJ Ma) and post-tectonic porphyritic monzogranites (2601ᆢ Ma). Ar-Ar hornblende ages for mafic schists from different areas within the greenstone belt wall rocks range between 2621 and 2498 Ma and have been interpreted to indicate mixing between metamorphic ages and cooling ages. The data support a geological model whereby volcanism and sedimentation are associated with an early phase of regional deformation at ca. 2.64 Ga, which may have started earlier and lasted longer, and evolves into the voluminous emplacement of granites (now gneissic granites) in the batholiths at approximately 2.62 Ga. Emplacement of post-tectonic tabular monzogranites takes place at ca. 2.60 Ga.     

Comparative Re-Os systematics of chondrites: Implications regarding early solar system processes

A suite of 47 carbonaceous, enstatite, and ordinary chondrites are examined for Re-Os isotopic systematics. There are significant differences in the ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os ratios of carbonaceous chondrites compared with ordinary and enstatite chondrites. The average ¹⁸⁷Re/¹⁸⁸Os for carbonaceous chondrites is 0.392 ± 0.015 (excluding the CK chondrite, Karoonda), compared with 0.422 ± 0.025 and 0.421 ± 0.013 for ordinary and enstatite chondrites (1σ standard deviations). These ratios, recast into elemental Re/Os ratios, are as follows: 0.0814 ± 0.0031, 0.0876 ± 0.0052 and 0.0874 ± 0.0027, respectively. Correspondingly, the ¹⁸⁷Os/¹⁸⁸Os ratios of carbonaceous chondrites average 0.1262 ± 0.0006 (excluding Karoonda), and ordinary and enstatite chondrites average 0.1283 ± 0.0017 and 0.1281 ± 0.0004, respectively (1σ standard deviations). The new results indicate that the Re/Os ratios of meteorites within each group are, in general, quite uniform. The minimal overlap between the isotopic compositions of ordinary and enstatite chondrites vs. carbonaceous chondrites indicates long-term differences in Re/Os for these materials, most likely reflecting chemical fractionation early in solar system history.A majority of the chondrites do not plot within analytical uncertainties of a 4.56-Ga reference isochron. Most of the deviations from the isochron are consistent with minor, relatively recent redistribution of Re and/or Os on a scale of millimeters to centimeters. Some instances of the redistribution may be attributed to terrestrial weathering; others are most likely the result of aqueous alteration or shock events on the parent body within the past 2 Ga.The ¹⁸⁷Os/¹⁸⁸Os ratio of Earth’s primitive upper mantle has been estimated to be 0.1296 ± 8. If this composition was set via addition of a late veneer of planetesimals after core formation, the composition suggests the veneer was dominated by materials that had Re/Os ratios most similar to ordinary and enstatite chondrites.     

Experimental validation of the wavefield transform of electromagnetic fields

The wavefield transform is a mathematical technique for transforming low-frequency electromagnetic (EM) signals to a non-diffusive wave domain. The ray approximation is valid in the transform space and this makes traveltime tomography for 3D mapping of the electrical conductivity distribution in the subsurface possible. The transform, however, imposes stringent frequency bandwidth and signal-to-noise ratio requirements on the data. Here we discuss a laboratory scale experiment designed to collect transform quality EM data, and to demonstrate the practical feasibility of transforming these data to the wavefield domain.
We have used the scalable nature of EM fields to design a time-domain experiment using graphite blocks to simulate realistic field conditions while leaving the time scale undisturbed. The spatial dimensions have been scaled down by a factor of a thousand by scaling conductivity up by a factor of a million. The graphite blocks have two holes drilled into them to carry out cross-well and borehole-to-surface experiments. Steel sheets have been inserted between the blocks to simulate a conductive layer.
Our experiments show that accurate EM data can be recorded on a laboratory scale model even when the scaling of some features, such as drill-hole diameters, is not maintained. More importantly, the time-domain EM data recorded in cross-well and surface-to-borehole modes can be usefully and accurately transformed to the wavefield domain. The observed wavefield propagation delay is proportional to the direct distance between the transmitter and receiver in a homogeneous medium. In a layered medium, data accuracy is reduced and, hence, our results are not so conclusive. On the basis of the experimental results we conclude that the wavefield transform could constitute a valid approach to the interpretation of accurate, undistorted time-domain data if further improvement in the transform can be realized.     

Focused ion beam technique and transmission electron microscope studies of microdiamonds from the Saxonian Erzgebirge, Germany

A focused ion beam of Ga ions is a relatively new technique that has been developed for microelectronic industries. Now researchers of the Earth sciences find it to be a promising tool for studying various geological materials. Using the FIB technique and an FEI Strata DB 235 dual beam system, we have successfully prepared several electron-transparent foils, which crossed μm-sized diamonds included in host minerals such as zircon and garnet from quartzofeldspathic rocks of the Saxonian Erzgebirge, Germany. Scanning and transmission electron microscopy applied to these foils revealed that the diamonds contain crystalline nanometric inclusions. These inclusions consist of minerals of known stoichiometries such as SiO₂ and Al₂SiO₅, whereas others are characterized by different combinations of Si, K, P, Ti, and Fe in the presence of oxygen (stoichiometries are not clear at this stage of research). One suite of inclusions is assumed to be represented by archerite, KH₂PO₄, which is known to be stable at pressures of 4–22 GPa, and one nanocrystal containing Pb, oxygen and carbon is interpreted to be Pb_xO_y or PbCO₃. Along with solid crystalline inclusions, the diamonds contain cavities filled by liquid/gas that escaped during sample preparation. These are associated with dislocations of diamond growth. Our data are consistent with the concept of diamond crystallization from a COH-rich multicomponent supercritical fluid and suggest that the composition of such a fluid is more consistent with a local crustal source rather than that of a mantle origin.     

Metal island growth and dynamics on molybdenite surfaces

In order to understand the adsorption mechanism of metal atoms to semiconducting surfaces, we have studied, as a model system, the vapor phase adsorption of Ag, Au, and Cu on the (001) surface of molybdenite (MoS₂) and the subsequent surface diffusion of these adsorbates. Our scanning tunneling microscopy (STM) images show that, depending on the type of metal atom that is adsorbed, islands of a characteristic size (2 nm for Ag, 8 to 10 nm for Cu, two distinct sizes of 2 nm and 8 to 10 nm for Au), shape (well rounded in the lateral extension) and thickness (one monolayer for Ag, 1 to 1.5 nm for Cu) are formed during the initial stages of deposition. Whole islands are observed to surface diffuse without loss of size or shape. Despite the relatively large size of the copper islands on molybdenite, these islands surface diffuse extensively, suggesting that the Cu-S interaction is weak. Surface diffusion is only hindered once individual islands start to coalesce. As copper islands accumulate, the size and shape of the original islands can still be recognized, supporting the conclusion that these characteristics are constant and that monolayer growth occurs by the aggregation of islands across the surface.The strength and the nature of the Ag-S(MoS₂) bond were further investigated by using molecular orbital calculations, ultraviolet photoelectron spectroscopy (UPS) and scanning tunneling spectroscopy (STS). By applying quantum mechanical approaches using a two-dimensional periodic molybdenite slab and hexagonal MoS₂ clusters of different sizes with metal atoms adsorbed to them, it is possible to calculate the electron transfer between the mineral surface and the metal atom as well as the adsorption energy as a function of surface coverage. In addition, we used the results from the quantum mechanical runs to derive empirical potentials that model the characteristics of the forces within the crystal, within the adsorbed islands, and the metal and mineral surface. The combination of quantum mechanical calculations and empirical force field calculations explain the electronic structure and the highest stability of Ag islands that have seven atoms in diameter, which exactly agrees with the size of experimentally observed islands. UPS results also suggest that a specific new state is formed (approximately 4.5 eV into the valence band) which may describe the Ag-S bond because it does not occur in pure silver or molybdenite.This study shows how the combination of microscopic (STM), spectroscopic (STS, UPS), compositional (X-ray photoelectron spectroscopy, XPS) and molecular modeling (quantum mechanical and empirical) techniques is a useful approach to understand the nature of the metal to sulfide bond. Further insights may be gained concerning the natural association of certain metals with sulfides.