Release of bound aromatic hydrocarbons from late Archean and Mesoproterozoic kerogens via hydropyrolysis

Hydrogen-lean kerogens (atomic H/C<0.4) isolated from the 2.5-billion-year-old (Ga) Mt. McRae Shale, Hamersley Group, at Tom Price, Western Australia, were studied via hydropyrolysis, a continuous-flow technique that degrades organic matter in a stream of high-pressure hydrogen assisted by a dispersed Mo catalyst. The hydropyrolysates yielded predominantly phenanthrene and pyrene, and higher polyaromatic hydrocarbons and alkylated homologues were generated in low relative concentrations. Saturated hydrocarbons were not detected. The molecular and carbon isotopic compositions of the hydropyrolysates are very similar to aromatic hydrocarbons obtained by solvent extraction of the host rocks. Because molecular structures covalently attached to kerogen are unaffected by contamination, this indicates that both the bound and extractable aromatic fractions are syngenetic with the host rocks. Therefore, the results of the hydropyrolysis experiments provide compelling evidence for preserved bitumen of Archean age. The very high proportion of nonalkylated polyaromatic hydrocarbons in the hydropyrolysates is consistent with hydrothermal dehydrogenation of the kerogen, and a marked concentration difference of pyrene in rock extracts and hydropyrolysates might be explained by hydrothermal redistribution of the bitumen. The kerogen and bitumen composition is therefore consistent with models suggesting a hydrothermal origin for the giant iron ore deposits at Mt. Tom Price. Comparison of the Archean samples with hydropyrolysates from immature Mesoproterozoic kerogens from the Roper Group, McArthur Basin, Northern Territory, and with pyrolysis experiments on Proterozoic kerogens in the literature suggests that Precambrian kerogens are frequently highly aromatic and lipid-poor regardless of their degree of thermal preservation.     

Geo-ontology Tools: The Missing Link

Numerous authors have presented ontology building tools that have all been developed as part of academic projects and that are usually adaptations of more generic tools for geo-spatial applications. While we trust that these tools do their job for the special purpose they have been built, the GIScience user community is still a long way away from off-the-shelf ontology builders that can be used by GIS project managers. In this article, we present a comparative study of ontology building tools described in some twenty peer-reviewed GIScience journal articles. We analyze them from the perspective of two application domains, crime analysis and transportation/land use. For the latter, we developed a database schema, which is substantially different from the three main templates commonly used. The crime analysis application uses a rule base for an agent-based model that had no precursor. In both cases, the currently available set of tools cannot replace manual coding of ontologies for use with ESRI-based application software. Based on these experiences, we outline a requirements list of what the tools described in the first part of the article are missing to make them practical from an applications perspective. The result is an R&D agenda for this important aspect of GIScience.     

Time dependent deformations during tunnelling and stability of tunnel faces in fine-grained soils under groundwater

The measures required for driving a tunnel below the groundwater table depend on the permeability of the soil. In coarse-grained, highly permeable soils additional measures, for example compressed-air support combined with a reduction of the permeability of the soil, e.g. induced by grouting, are necessary. Compared to this, it is possible to do without such measures in fine-grained, cohesive soils because of the increased short-term stability of the tunnel face under undrained conditions. In this publication the results of 3-dimensional finite-element calculations are presented to show the influence of the permeability of the soil and also the rate of the tunnel driving on the deformations around the tunnel as well as on the ground surface. The calculated deformations can furthermore be considered as an indicator for the time dependent stability of the tunnel face due to a higher redistribution of stresses and by that an enlargement of the plasticized zone. Usually the stability of the tunnel face is reduced by the presence of water because of the flow of water towards the tunnel. In low permeable soils undrained conditions prevail immediately after an excavation step. In this case relatively high stability-ratios may occur. The stability of the tunnel face will be reduced with increasing time until reaching the lower boundary of possible values, possibly leading to failure. If calculations are done under the assumption of drained conditions, the real stability of the tunnel face during construction may substantially exceed that of the calculated one. On the other hand, if calculations are done for undrained conditions, the effective stability may lie on the unsafe side [10]. There is therefore a big demand to optimize the method of investigating deformations around the tunnel, so as to ensure a safe tunnel excavation on the one hand and to guarantee a cost-effective process on the other. In this paper the tunnelling process is modelled by a step-by-step excavation under atmospheric conditions. The soil is described by a material model which distinguishes between primary and unload-reload stress paths and also accounts for stress-dependent stiffness parameters. The failure criterion is described by the Mohr-Coulomb criterion that considers cohesion, friction angle and angle of dilatancy.     

Discovery of the high-field polar RX J1724.0+4114

We report the discovery of a new AM Herculis binary (polar) as the optical counterpart of the soft X-ray source RX J1724.0+4114 detected during the ROSAT all-sky survey. The magnetic nature of this V  ∼ 17 mag object is confirmed by low-resolution spectroscopy showing strong Balmer and He  II emission lines superimposed on a blue continuum, which is deeply modulated by cyclotron humps. The inferred magnetic field strength is 50 ± 4 MG (or possibly even ≈ 70 MG). Photometric observations spanning ∼ 3 yr reveal a period of 119.9 min, directly below the period gap. The morphology of the optical and X-ray light curves, which do not show eclipses by the secondary star, suggests a self-eclipsing geometry. We derive a lower limit on the distance of d  ≳ 250 pc.     

Measurements of Volatile Organic Compounds (VOC) During POPCORN 1994: Applying a New On-Line GC–MS-Technique

Atmospheric concentrations of ca. 250 C6–C15 hydrocarb on and C4–C12 oxygenated volatile organic compounds (VOC) including alkanes, benzene and alkyl benzenes, monoterpenes and aldehydes were measured in August 1994 during the POPCORN campaign (POPCORN = Photo-Oxidant formation by Plant emitted Compounds and OH Radicals in North-Eastern Germany). About 80 substances together contributed 90% of the atmospheric carbon in this range of molecular weight. During this field campaign VOC-emissions from several crop and tree species and the ambient concentrations of CO, C2–C7 non-methane hydrocarbons (NMHC), C1 and C2 aldehydes, nitrogen oxides, ozone and hydroxyl-radicals (OH) were also measured. These data were used to interpret the VOC measurements presented here. The on-line GC–MS used for the VOC measurements combines adsorptive sampling with thermal desorption and GC–MS analysis in an automated system. Internal standards were used to quantify the measurements. Ozone was destroyed prior to the sample preconcentration through the gas phase reaction with NO. Aromatic compounds like benzene, toluene and xylenes were the most abundant compound class among the measured substances, -pinene and 3-carene, most probably originating from pineforests ca. 1 km away from the measuring site, were the most abundant monoterpenes. The highest mixing ratios of most compounds were measured in nights with strong inversion situations. The toluene mixing ratios then reached 630 pptv; -pinene mixing ratios went up to 430 pptv. The median of all toluene and -pinene measurements during the campaign was 125 pptv or 22 pptv, respectively. These values are on the lower end of ambient measurements reported for continental sites. In most samples also n-pentanal, n-hexananl, n-nonanal and n-undecanal were present. Median mixing ratios were 9, 16, 14 and 8 pptv, respectively. Emission studies indicate that these highly reactive compounds are most probably emitted from maize. It is shown by a simple first order approach that the potential for ozone formation during the POPCORN campaign was roughly equal for anthropogenic and biogenic VOC. From measured concentrations of ozone, OH-radicals, methane, CO, C2–C15 nonmethane hydrocarbons (NMHC) and C5–C11 aldehydes a photochemical production of ozone in the order of 3.5 ppb/h can be estimated. Apart from formaldehyde and acetaldehyde, which are at least partly products of VOC oxidation, the substance group with the largest contribution to the VOC turnover are the monoterpenes. They contribute ca. 30%. However, the mechanism of terpene oxidation is very complex and presently only partly understood. Thus the actual contribution of monoterpenes to ozone formation is very uncertain. Other measured compound classes such as light alkenes, alkanes, aromatics, and C5–C11 aldehydes contribute each between 10% and 15% to ozone formation. The measuring site was not influenced directly from strong biogenic or anthropogenic sources, and the results obtained during the POPCORN campaign can be regarded as a typical picture of a remote rural central European environment.     

Late Maastrichtian litho- and ecocycles from hemipelagic deposits of eastern Sinai, Egypt

A biostratigraphical and palaeoecological survey employing calcareous nannofossils and planktonic and benthonic foraminifera has been carried out in four sections of hemipelagic marls and chalks of the Late Maastrichtian Abathomphalus mayaroensis Zone of eastern Sinai, in order to evaluate the mechanisms controlling the composition of the well preserved microfauna and nannoflora.The Abathomphalus mayaroensis Zone in eastern Sinai can be easily identified by the wide occurrence of the index fossil A. mayaroensis and can be further subdivided by the first occurrences of Plummerita reicheli (ex. P. hantkeninoides) and Micula prinsii. Microfossil abundances and lithologies are characterised by pronounced repetitive distribution patterns. These include low and high frequency fluctuations of the planktonic/benthonic (P/B) foraminiferal ratio, repetitive changes in the abundance of calcareous nannofossils and benthonic foraminifera, as well as the development of chalk-marl couplets and thinning upward chalk packets. both microfossil distribution patterns and the occurrence of rhythmites are attributed to changes in primary palaeoproductivity. Semiquantitative investigations of calcareous nannofossils and a few selected benthonic foraminifera yield evidence of the presence of high (HP) and low (LP) productivity assemblages.The interpreted HP assemblage is dominated by Glaukolithus diplogrammus, Manvitella pemmatoidea, Microrhabdulus decoratus and Micula murus and the benthonic foraminifera Neoflabellina jarvisi; the LP assemblage is characterised by Lithraphidites quadratus and Bolivinoides draco. However, further quantitative studies are necessary to reconstruct the exact composition of these assemblages and to explain deviatory developments. The chalk-marl couplets, thinning-upward chalk packets and the high frequency P/B patterns are interpreted to reflect productivity changes related to orbital forcing. These hemipelagites were deposited during the latest phase of the southern Tethyan upwelling system, which was active from the Santonian to the Late Maastrichtian with a peak in the Campanian. Termination of upwelling just before the K/T boundary also provides a good explanation for the change towards a palaeobathymetric control on foraminiferal distribution, as observed for the Palaeocene of central east Sinai.     

The role of fluids in partitioning brittle deformation and ductile creep in auriferous shear zones between 500 and 700 °C

The fabric, mineralogy, geochemistry, and stable isotope systematics of auriferous shear zones in various hydrothermal gold deposits were studied in order to discuss the role of fluids in rock deformation at temperatures between 500 °C and 700 °C. The strong hydrothermal alteration and gold mineralization indicates that effective permeability development goes ahead with high-temperature rock deformation. The economic gold enrichment is often hosted by breccias and quartz veins in the ductile shear zones, which either formed at fast strain rates or by low strain continuous deformation at slow strain rates. Both processes require (1) a close-to lithostatic to supralithostatic fluid pressure and/or (2) a strong rheology contrast of the deformed lithologies that is often developed during progressive hydrothermal alteration. Compartments of high fluid pressure are sealed from the rest of the shear zones by high-temperature deformation mechanisms, e.g. intracrystalline plasticity and diffusion creep, and compaction. In contrast, in mylonites with heterogeneous crystal plastic and brittle deformation mechanisms for the various minerals, an interconnected network of a grain-scale porosity forms an effective fluid conduit, which hampers fluid pressure build-up and the formation of veins.The auriferous shear zones of the various gold mines represent fluid conduits in the deeper crust, 100 m along strike and up to 1000 m down-dip. The hydrothermal fluids infiltrated may be responsible for low magnitude earthquakes in the Earth's lower crust, which otherwise deforms viscously.