The role of the Kupferschiefer in the formation of hydrothermal base metal mineralization in the Spessart ore district, Germany: insight from detailed sulfur isotope studies

The Spessart district (SW Germany), located at the southwestern margin of the Permian Kupferschiefer basin in Central Europe, hosts abundant stratabound and structurally controlled base metal mineralization. The mineralization styles identified are (1) stratabound Cu-Pb-Zn-(Ag) ores in Zechstein sedimentary rocks, (2) structurally controlled Cu-As-(Ag) ores in Zechstein sedimentary rocks, (3) crosscutting Co-Ni-(Bi)-As and Cu-Fe-As veins, (4) stratabound metasomatic Fe-Mn carbonate ores in Zechstein dolomite, (5) barren barite veins, and (6) Fe-Mn-As veins in Permian rhyolites. Building on previous work that involved mineralogical, textural, and chemical characterization of the major mineralization types, we have performed a comprehensive sulfur isotope study that applied both conventional and novel laser-ablation multi-collector inductively coupled plasma mass spectrometry techniques. The δ³⁴S values of sulfide minerals from the different ore types are consistently negative and highly variable, in the range between −44.5‰ and −3.9‰, whereas the δ³⁴S values of barite are all positive in the range between 4.7‰ and 18.9‰. Remarkably, stratabound and structurally controlled mineralization in Zechstein sedimentary rocks has the least negative δ³⁴S values, whereas vein-type deposits have consistently more negative δ³⁴S values. The observed pattern of sulfide δ³⁴S values can be best interpreted in terms of fluid mixing at the basement-cover interface. Hydrothermal fluids originating from the crystalline basement migrated upward along subvertical fault zones and were periodically injected into groundwaters that were flowing in the post-Variscan sedimentary cover. These groundwaters had interacted with the Zechstein sedimentary rocks, resulting in fluids characterized by elevated concentrations of reduced sulfur (with negative δ³⁴S values) and alkaline pH. Repeated mixing between both chemically contrasting fluids caused rapid and efficient precipitation of sulfide ore minerals in hydrothermal veins with highly variable but distinctly negative δ³⁴S values.     

Comparative organic petrology of interlayered sandstones,siltstones, mudstones and coals in the Upper Carboniferous Ruhr basin,Northwest Germany,and their thermal history and methane generation

In the coal-mining Ruhr-area, Upper Carboniferous rocks (ca. 4000 m) consist of interlayered sandstones, siltstones, mudstones and coals. They were deposited in a tropical, paralic environment where alternating fluvial sedimentation, occasional marine ingressions, and swamp growth resulted in an irregular cyclic succession. The total sedimentary package contains on an average 6 Vol.-% of organic matter. About 70 Vol.-% of the organic matter occurs in coal seams, the rest as dispersed organic matter in clastic rocks. The organic matter is autochthonous in the coals and allochthonous in associated sandstones and siltstones. It consists of about 70% vitrinite, 20% inertinite, and 10% liptinite. The overall maceral group composition is the same for coals and dispersed organic matter. This surprising similarity is caused by a nearly exclusive input of land-plant derived organic matter to swamps and fluvial systems and a similar degree of preservation. Highest average liptinite contents (% of total macerals) were found in unrooted mudstones, highest average inertinite contents in coarse-grained siltstones and highest average vitrinite percentages in sandstones.Maturities of the sediments studied are well within the hydrocarbon generation window, e. g. vitrinite reflectivities range from 0.6% to 1.6%. Reflectivities measured on dispersed particles in clastic rocks are similar to those measured in coal seams. Calculations of the amount of methane generated indicate that coal seams contributed more to the total hydrocarbon generation than dispersed organic matter.

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Zusammenfassung Das Oberkarbon des Ruhrgebietes besteht aus ca. 4000 Metern wechsellagernder Sandsteine, Siltsteine und Kohleflöze. Der Ablagerungsraum der Sedimente war eine Region mit tropischem Klima, genauer ein paralisches Environment mit unregelmäßig alternierenden Folgen von fluviatilen Sedimenten, marinen Transgressionen und verbreiteten Sumpfablagerungen. Der Anteil organischer Substanzen an der gesamten Sedimentmenge beträgt durchschnittlich 6%. 70% dieser organischen Masse ist in Kohleflözen angereichert, der Rest liegt verteilt in den klastischen Gesteinen vor. Die Herkunft der organischen Substanz in den Kohleflözen ist autochthon, die in den benachbarten Sand- und Siltsteinen allochton. Die Zusammensetzung des organischen Materials ist 70% Vitrinit, 20% Inertinit und 10% Liptinit. Die allgemeine Zusammensetzung nach Mazeral-Gruppen ist für die Kohleflöze und das verteilte Material in den Nachbargesteinen identisch. Diese Ähnlichkeit beruht auf der gemeinsamen Herkunft der organischen Substanz in Sümpfen und Flußsystemen, die fast ausschließlich von Landpflanzen bestimmt wird, und einer sich entsprechenden Konservierung.Der Reifegrad der analysierten Sedimente liegt innerhalb des Kohlenwasserstoff-Bildungsbereiches (die Vitrinit-Reflexionen reichen von 0,6–1,6%). Dabei entsprechen die in den klastischen Gesteinen beobachteten Reflexionswerte weitgehend denen der Kohleflöze. Anhand der Menge des erzeugten Methans läßt sich erkennen, daß der Anteil der Kohleflöze an der Kohlenwasserstoff-Produktion höher ist als der Anteil, den disperse organische Substanzen der Klastika beisteuern.

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Résumé Dans la région minière de la Ruhr, le Carbonifère supérieur constitue une succession, épaisse de 4.000 m environ, de grès, de siltites et de charbon. Leur dépôt, dans un milieu paralique tropical, a été marqué par des alternances de sédimentation fluiviale, de transgressions marines occasionnelles, et d'épisodes marécageux; il en résulte une disposition cyclique irrégulière. La série sédimentaire contient dans l'ensemble 6% de matière organique en moyenne. Environ 70% de cette matière organique se trouve dans les couches de charbon où elle est autochtone; le reste est allochtone et dispersé dans les grès et siltites. La matière organique se répartit approximativement en 70% de vitrinite, 20% d'inertinite et 10% de liptinite. La composition moyenne du groupe «macéral» est la même pour les charbons et la matière organique dispersée. Cette identité surprenante est l'expression d'une alimentation provenant exclusivement de plantes terrestres et d'un même degré de conservation.La maturité des sédiments étudiés se situe à l'intérieur du domaine de genèse des hydrocarbures: le pouvoir réflecteur de la vitrinite s'échelonne entre 0,6% et 1,6%. Les gradients du pouvoir réflecteur observés dans les roches détritiques et dans les couches de charbon sont analogues. Le calcul de la quantité de méthane engendré indique que la contribution des couches de charbon à la production totale d'hydrocarbure est supérieur à celle de la matière organique dispersée.

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Composition of organic matter in subducted and unsubducted sediments off the Nicoya peninsula, Costa Rica (ODP Leg 170, Sites 1039 and 1040)

Investigation of sediment samples from Sites 1039 and 1040 (ODP Leg 170) drilled off the Nicoya peninsula (Costa Rica) by organic geochemical and organic petrological methods has revealed that subduction has only little influence on the composition of the sedimentary organic matter. Organic carbon contents reached 1.5% in the Pleistocene samples but Miocene and Pliocene sediments had an average organic carbon content of less than 0.5%. Organic carbon/sulfur ratios are generally below 2.8, reflecting an intense sulfate reduction in the uppermost sediments which was enhanced by sulfate supply both from sea water and deeper strata. Microscopical examinations indicate that the organic matter is mainly derived from marine sources. A small amount of terrigenous organic matter is, however, present as well according to n-alkane and fatty acid distributions. The alkenone unsaturation index U₃₇^k′ shows only a slight decrease during the Miocene and Pliocene, and stronger variations in the Pleistocene, probably indicating more stable sea surface temperatures during the Miocene and Pliocene. Variations in the Pleistocene can possibly be related to glacial/interglacial changes.     

Emission of nitrous oxide from temperate forest soils into the atmosphere

N₂O emission rates were measured during a 13-month period from July 1981 till August 1982 with a frequency of once every two weeks at six different forest sites in the vicinity of Mainz, Germany. The sites were selected on the basis of soil types typical for many of the Central European forest ecosystems. The individual N₂O emission rates showed a high degree of temporal and spatial variabilities which, however, were not significantly correlated to variabilities in soil moisture content or soil temperatures. However, the N₂O emission rates followed a general seasonal trend with relatively high values during spring and fall. These maxima coincided with relatively high soil moisture contents, but may also have been influenced by the leaf fall in autumn. In addition, there was a brief episode of relatively high N₂O emission rates immediately after thawing of the winter snow. The individual N₂O emission rates measured during the whole season ranged between 1 and 92 g N₂O-N m^–2 h^–1. The average values were in the range of 3–11 g N₂O-N m^–2 h^–1 and those with a 50% probability were in the range of 2–8 g N₂O-N m^–2 h^–1. The total source strength of temperate forest soils for atmospheric N₂O may be in the range of 0.7–1.5 Tg N yr^–1.     

Population dynamics and natural hazard risk management: conceptual and practical linkages for the case of Austrian policy making

Natural Hazards - This contribution explores the conceptual and empirical linkages between population dynamics and natural hazard risk management (NHRM). Following a review of the international...     

Organic sedimentary deposits in Titan’s dry lakebeds: Probable evaporite

We report the discovery of organic sedimentary deposits at the bottom of dry lakebeds near Titan’s north pole in observations from the Cassini Visual and Infrared Mapping Spectrometer (VIMS). We show evidence that the deposits are evaporitic, making Titan just the third known planetary body with evaporitic processes after Earth and Mars, and is the first that uses a solvent other than water.     

Application of the water balance model J2000 to estimate groundwater recharge in a semi-arid environment: a case study in the Zarqa River catchment, NW-Jordan

Pollution and overexploitation of scarce groundwater resources is a serious problem in the Zarqa River catchment, Jordan. To estimate this resource’s potential, the amount and spatial distribution of groundwater recharge was calculated by applying the hydrological model J2000. The simulation period is composed of daily values gathered over a 30-year period (July 1977 to June 2007). The figure finally obtained for estimated groundwater recharge of the Zarqa River catchment is 105 × 10⁶ m³ per year (21 mm a^?1). This is 19 % higher than the value previously assumed to be correct by most Jordanian authorities. The average ratio of precipitation to groundwater recharge is 9.5 %. To directly validate modelled groundwater recharge, two independent methods were applied in spring catchments: (1) alteration of stable isotope signatures (δ¹⁸O, δ²H) between precipitation and groundwater and (2) the chloride mass balance method. Recharge rates determined by isotopic investigations are 25 % higher, and recharge rates determined by chloride mass balance are 9 % higher than the modelled results for the corresponding headwater catchments. This suggests a reasonably modelled safe yield estimation of groundwater resources.     

Nitrogen recycling in subducted oceanic lithosphere: The record in high- and ultrahigh-pressure metabasaltic rocks

This paper provides the first measurements of the nitrogen (N) concentrations and isotopic compositions of high- and ultrahigh-pressure mafic eclogites, aimed at characterizing the subduction input flux of N in deeply subducting altered oceanic crust (AOC). The samples that were studied are from the Raspas Complex (Ecuador), Lago di Cignana (Italy), the Zambezi Belt (Zambia) and Cabo Ortegal (Spain), together representing subduction to 50-90 km depths. The eclogites contain 2-20 ppm N with δ¹⁵N_air values ranging from −1 to +8‰. These values overlap those of altered oceanic crust, but are distinct from values for fresh MORB (for the latter, ∼1.1 ppm N and δ¹⁵N_air ∼ −4‰). Based on N data in combination with other trace element data, the eclogite suites can be subdivided into those that are indistinguishable from their likely protolith, AOC, with or without superimposed effects of devolatilization (Lago di Cignana, Cabo Ortegal), and those that have experienced metasomatic additions during subduction-zone metamorphism (Zambezi Belt, Raspas). For the former group, the lack of a detectable loss of N in the eclogites, compared to various altered MORB compositions, suggests the retention of N in deeply subducted oceanic crust. The metasomatic effects affecting the latter group can be best explained by mixing with a (meta)sedimentary component, resulting in correlated enrichments of N and other trace elements (in particular, Ba and Pb) thought to be mobilized during HP/UHP metamorphism. Serpentinized and high-pressure metamorphosed peridotites, associated with the eclogites at Raspas and Cabo Ortegal, contain 3-15 ppm N with δ¹⁵N_air values ranging from +3 to +6‰, significantly higher than the generally accepted values for the MORB mantle (δ¹⁵N_air ∼ −5‰). Based on their relatively high N contents and their homogeneous and positive δ¹⁵N values, admixing of sedimentary N is also indicated for the serpentinized peridotites.One possible pathway for the addition of sediment-derived N into eclogites and peridotites involves mixing with fluids along the slab-mantle wedge interface. Alternatively, sedimentary N could be incorporated into peridotites during serpentinization at bending-related faults at the outer rise and, during later deserpentinization, released into fluids that then infiltrate overlying rocks. Deep retention of N in subducting oceanic crust should be considered in any attempt to balance subduction inputs with outputs in the form of arc volcanic gases. If materials such as these eclogites and serpentinized peridotites are eventually subducted to beyond sub-arc depths into the deeper mantle, containing some fraction of their forearc-subarc N inventory (documented here), they could deliver isotopically heavy N into the mantle to potentially be sampled by plume-related magmas.     

Integrated 3D forward stratigraphic and petroleum system modeling of the Levant Basin,Eastern Mediterranean

The Eastern Mediterranean Levant Basin is a proven hydrocarbon province with recent major gas discoveries. To date, no exploration wells targeted its northern part, in particular the Lebanese offshore. The present study assesses the tectono‐stratigraphic evolution and related petroleum systems of the northern Levant Basin via an integrated approach that combines stratigraphic forward modeling and petroleum systems/basin modeling based on the previous published work. Stratigraphic modeling results provide a best‐fit realisation of the basin‐scale sedimentary filling, from the post‐rift Upper Jurassic until the Pliocene. Simulation results suggest dominant eastern marginal and Arabian Plate sources for Cenozoic siliciclastic sediments and a significant contribution from the southern Nilotic source mostly from Lower Oligocene to Lower Miocene. Basin modeling results suggest the presence of a working thermogenic petroleum system with mature source rocks localised in the deeper offshore. The generated hydrocarbons migrated through the deep basin within Jurassic and Cretaceous permeable layers towards the Latakia Ridge in the north and the Levant margin and offshore topographic highs. Furthermore, the basin model indicates a possibly significant influence of salt deposition during Messinian salinity crisis on formation fluids. Ultimately, the proposed integrated workflow provides a powerful tool for the assessment of petroleum systems in underexplored areas.