Structure and origin of terpenoid hydrocarbons in some German coals

Hydrocarbon extracts of coal samples from major coal fields in West Germany have been investigated by gas chromatography-mass spectrometry (GC/MS). The samples are of Carboniferous and Tertiary age and derive from limnic and paralic environments, the Saar District, the Ruhr Area and the Lower Rhine Basin.Differences in facies, maturity and age reflected in the distribution patterns of the extracted alkylcyclohexanes. An unexpected occurrence of cyclic diterpenoid hydrocarbons in some samples of Carboniferous age has been found. The tetracyclic compounds mainly show phyllocladane type structures and can serve as source indicators.Hydrocarbons obtained from chemical degradation of the macromolecular material of the samples also revealed phyllocladane-type compounds which are normally associated to resins of modern and extinct familes of conifers. Origin and structural variations of this class of hydrocarbons are discussed in terms of maturity and palaeobotanical implications.     

Identifying low-temperature hydrothermal karst and palaeowaters using stable isotopes: a case study from an alpine cave,Entrische Kirche,Austria

The area south of the prominent east–west trending Salzach Valley at the northern rim of the Central Alps of Austria has long been known to host anomalously warm springs emerging from a highly deformed calcite marble (Klammkalk). This unit also hosts cavities whose shapes suggest a hydrothermal karst origin and which are lined by calcite spar. We report here petrographic and isotopic evidence suggesting that dissolution by ascending low-temperature thermal waters also played an important role in the origin of a large cave in this region, Entrische Kirche. A paleo cave wall, preserved behind a thick flowstone in the interior of this cave, revealed a brownish bleaching zone which contrasts to the medium grey colour of the unaltered marble beneath. Across this zone the C and O isotope values gradually decrease by 3 and 11‰, respectively. These compositions are very different from those of the speleothem above but are similar to phreatic calcite spar from hydrothermal karst cavities in other outcrops in the area, where the absence of two-phase fluid inclusions suggests a low-temperature (less than ca. 50°C) hydrothermal origin. U/Th dating of the flowstone capping the alteration zone yielded a minimum age of the thermal water invasion in Entrische Kirche of ca. 240 kyr. There is no evidence in Entrische Kirche that these palaeowaters reached the point of calcite precipitation, but it is physically conceivable that higher and as yet unexplored parts of this deep (ca. 900 m) cave contain cavities lined by phreatic cave spar.     

上部地壳的流体作用与大理岩的低温塑性

本文应用光学显微镜、透射电子显微镜和阴极发光显微镜系统研究了Ｗａｔｅｒｂｅｒｇ断层带（纳米比亚）内粗晶大理岩中发育的构造岩,宏观碎裂结构与微观糜棱装结构是断层构造岩的主要特点。巨大的孪形碎屑与弥漫的细小粒质形成了鲜明的反差,广泛发育的压溶颖合线与多阶段方解石细脉遍布构造带不同部位,ＴＥＭ亚微粒粒度具有简单的峰值分布（～０．３～０．４μｍ）,但动态重结晶颗粒的粒度却具有较大的变化范围（０．１～３．０     

The accessibility of nodes in the Belgian road network

This paper presents an analysis of the accessibility of nodes in the Belgian road network. The intersection of roads are considered as the nodes and their connecting roads as the edges of a network. By means of the Dijkstra algorithm accessibility values are computed for each node by summing shortest travel times to a reference system of 158 nodes spread evenly over the Belgian territory. A comparison of the measured actual accessibility with that determined from an optimal situation provides an indication of the quality of directness of the Belgian road system. Accessibility and directness are shown cartographically. An isochronal map illustrates the access to Brussels.     

Long-Term Changes in Water Quality and Productivity in the Patuxent River Estuary: 1985 to 2003

We conducted a quantitative assessment of estuarine ecosystem responses to reduced phosphorus and nitrogen loading from sewage treatment facilities and to variability in freshwater flow and nonpoint nutrient inputs to the Patuxent River estuary. We analyzed a 19-year dataset of water quality conditions, nutrient loading, and climatic forcing for three estuarine regions and also computed monthly rates of net production of dissolved O₂ and physical transport of dissolved inorganic nitrogen (DIN) and phosphorus (DIP) using a salt- and water-balance model. Point-source loading of DIN and DIP to the estuary declined by 40–60% following upgrades to sewage treatment plants and correlated with parallel decreases in DIN and DIP concentrations throughout the Patuxent. Reduced point-source nutrient loading and concentration resulted in declines in phytoplankton chlorophyll-a (chl-a) and light-saturated carbon fixation, as well as in bottom-layer O₂ consumption for upper regions of the estuary. Despite significant reductions in seaward N transport from the middle to lower estuary, chl-a, turbidity, and surface-layer net O₂ production increased in the lower estuary, especially during summer. This degradation of water quality in the lower estuary appears to be linked to a trend of increasing net inputs of DIN into the estuary from Chesapeake Bay and to above-average river flow during the mid-1990s. In addition, increased abundance of Mnemiopsis leidyi significantly reduced copepod abundance during summer from 1990 to 2002, which favored increases in chl-a and allowed a shift in total N partitioning from DIN to particulate organic nitrogen. These analyses illustrate (1) the value of long-term monitoring data, (2) the need for regional scale nutrient management that includes integrated estuarine systems, and (3) the potential water quality impacts of altered coastal food webs.     

Modelling fractionation of stable isotopes in stalagmites

High resolution δ¹³C and δ¹⁸O profiles recorded in precisely dated speleothems are widely used proxies for the climate of the past. Both δ¹³C and δ¹⁸O depend on several climate related effects including meteorological processes, processes occurring in the soil zone above the cave and isotope fractionation processes occurring in the solution layer on the stalagmite surface. Here we model the latter using a stalagmite isotope and growth model and determine the relationship between the stable isotope values in speleothem calcite and cave parameters, such as temperature, drip interval, water p_CO2 and a mixing coefficient describing mixing processes between the solution layer and the impinging drop.The evolution of δ¹³C values is modelled as a Rayleigh distillation process and shows a pronounced dependence on the residence time of the solution on the stalagmite surface and the drip interval, respectively. The evolution of δ¹⁸O values, in contrast, is also influenced by buffering reactions between the bicarbonate in the solution and the drip water driving the δ¹⁸O value of the bicarbonate towards the value expected for equilibrium isotope fractionation between drip water and calcite. This attenuates the dependence of the δ¹⁸O values on drip interval. The temperature dependence of δ¹⁸O, however, is more pronounced than for δ¹³C and in a similar range as expected for fractionation under equilibrium conditions.We also investigate the isotopic enrichment of the δ¹³C and δ¹⁸O values along individual growth layers and, thus, the slopes expected for Hendy tests. The results show that a positive Hendy test is only possible if isotope fractionation occurred under disequilibrium conditions. However, a negative Hendy test does not exclude that isotope fractionation occurred under disequilibrium conditions. A more reliable indicator for disequilibrium fractionation is the enrichment of the δ¹³C values along an individual growth layer.     

X-ray absorption contrast images of binary chemical reactions

Low-divergence synchrotron-sourced X-rays enable a radiographic imaging scheme for full characterization of binary chemical reactions and characterization by type of more complex reactions, in situ, in diamond anvil cells (DAC). Spatially resolved reactants are induced to react by laser heating of their interface. The spatially intermediate products are observed through X-ray absorption contrast. Limits to the technique include the ability to maintain controlled experiment geometry during compression and the ability to resolve chemical differences between reactants and products by X-ray absorption. The ability to make in situ observations at experimental pressure and temperature obviates the problem with quenching techniques for capturing liquid compositions in experiments with dimensions smaller than the diffusion length during quenching time. Partially molten Fe-alloy systems, of poor quenchability, are examined at DAC pressures and temperatures for relevance to Earth's core constitution and evolution. Determinations of eutectic melting in Fe–FeS match known results. Of the probable light elements that may alloy with Fe in the Earth's liquid outer core, Fe–FeS experiments show only modest quenching problems, but C and Si alloy experiments are highly vulnerable to quenching artifacts. The observed reactivity of FeS, Fe₃C, FeSi, and FeO(OH) with Fe in DAC makes the observed non-reactivity between Fe and FeO more significant, reducing the probability that oxygen alone is the major alloy in Earth's molten outer core.     

Environmental Determinants of Emergent Macrophyte Vegetation in Pacific Northwest Estuarine Tidal Wetlands

We investigated whether within wetland environmental conditions or surrounding land cover measured at multiple scales were more influential in structuring regional vegetation patterns in estuarine tidal wetlands in the Pacific Northwest, USA. Surrounding land cover was characterized at the 100, 250, and 1,000 m, and watershed buffer scales. Vegetation communities were characterized by high species richness, lack of monotypic zonation, and paucity of invasive species. The number of species per site ranged between 4 and 20 (mean?±?standard deviation?=?10.2?±?3.1). Sites supported a high richness (mean richness of native species 8.7?±?2.8) and abundance of native macrophytes (mean relative abundance 85 %?±?19 %). Vegetation assemblages were dominated by a mix of grasses, sedges, and herbs with Sarcocornia pacifica and Distichlis spicata being common at sites in the oceanic zone of the estuary and Carex lyngbyei and Agrostis stolonifera being common at the fresher sites throughout the study area. The vegetation community was most strongly correlated with salinity and land cover within close proximity to the study site and less so with land cover variables at the watershed scale. Total species richness and richness of native species were negatively correlated with the amount of wetland in the buffer at all scales, while abundance of invasive species was significantly correlated to within wetland factors, including salinity and dissolved phosphorus concentrations. Landscape factors related to anthropogenic disturbances were only important at the 100-m buffer scale, with anthropogenic disturbances further from the wetland not being influential in shaping the vegetation assemblage. Our research suggests that the traditional paradigms of tidal wetland vegetation structure and environmental determinants developed in east coast US tidal wetlands might not hold true for Pacific Northwest wetlands due to their unique chemical and physical factors, necessitating further detailed study of these systems.     

Fluid evolution of the Hub Stock, Horní Slavkov–Krásno Sn–W ore district, Bohemian Massif, Czech Republic

The Horní Slavkov–Krásno Sn–W ore district is hosted by strongly altered Variscan topaz–albite granite (Krudum granite body) on the northwestern margin of the Bohemian Massif. We studied the fluid inclusions on greisens, ore pockets, and ore veins from the Hub Stock, an apical expression of the Krudum granite. Fluid inclusions record almost continuously the post-magmatic cooling history of the granite body from ～500 to <50°C. Rarely observed highest-temperature (～500°C) highest-salinity (～30?wt.% NaCl eq.) fluid inclusions are probably the result of secondary boiling of fluids exsolved from the crystallizing magma during pressure release which followed hydraulic brecciation of the gneissic mantle above the granite cupola. The greisenization was related to near-critical low-salinity (0–7?wt.% NaCl eq.) aqueous fluids with low amount of CO₂, CH₄, and N₂ (≤10?mol% in total) at temperatures of ～350–400°C and pressures of 300–530 bar. Crush-leach data display highly variable and negatively correlated I/Cl and Br/Cl values which are incompatible with both orthomagmatic and/or metamorphic origin of the fluid phase, but can be explained by infiltration of surficial and/or sedimentary fluids. Low fluid salinity indicates a substantial portion of meteoric waters in the fluid mixture that is in accordance with previous stable isotope data. The post-greisenization fluid activity associated with vein formation and argillitization is characterized by decreasing temperature (<350 to <50°C), decreasing pressure (down to ～50–100 bar), and mostly also decreasing salinity.     

New age constraints on the western Betic intramontane basins: A late Tortonian closure of the Guadalhorce Corridor?

Several gateways connected the Mediterranean with the Atlantic during the late Miocene but the timing of closure and therefore their role prior to and during the Messinian Salinity Crisis (5.97–5.33 Ma) is still under debate. The timing of closure of the Guadalhorce Corridor is especially disputed as the common lack of marine microfossils hampers precise age determination. Here we present new biostratigraphic age constraints on the sediments of the Ronda, Antequera and Arcos regions, which formed the northern part of the Guadalhorce Corridor. The general presence of Globorotalia menardii 4 in the youngest deep‐marine sediments of all three regions indicates a late Tortonian age, older than 7.51 Ma. We conclude that the Guadalhorce Corridor closed during the late Tortonian, well before the onset of the Messinian Salinity Crisis and that the late Tortonian tectonic uplift of the eastern Betics extended into the western Betics.