Oil-generation kinetics for organic facies with Type-II and -IIS kerogen in the Menilite Shales of the Polish Carpathians

The Menilite Shales (Oligocene) of the Polish Carpathians are the source of low-sulfur oils in the thrust belt and some high-sulfur oils in the Carpathian Foredeep. These oil occurrences indicate that the high-sulfur oils in the Foredeep were generated and expelled before major thrusting and the low-sulfur oils in the thrust belt were generated and expelled during or after major thrusting. Two distinct organic facies have been observed in the Menilite Shales. One organic facies has a high clastic sediment input and contains Type-II kerogen. The other organic facies has a lower clastic sediment input and contains Type-IIS kerogen. Representative samples of both organic facies were used to determine kinetic parameters for immiscible oil generation by isothermal hydrous pyrolysis and S₂ generation by non-isothermal open-system pyrolysis. The derived kinetic parameters showed that timing of S₂ generation was not as different between the Type-IIS and -II kerogen based on open-system pyrolysis as compared with immiscible oil generation based on hydrous pyrolysis. Applying these kinetic parameters to a burial history in the Skole unit showed that some expelled oil would have been generated from the organic facies with Type-IIS kerogen before major thrusting with the hydrous-pyrolysis kinetic parameters but not with the open-system pyrolysis kinetic parameters. The inability of open-system pyrolysis to determine earlier petroleum generation from Type-IIS kerogen is attributed to the large polar-rich bitumen component in S₂ generation, rapid loss of sulfur free-radical initiators in the open system, and diminished radical selectivity and rate constant differences at higher temperatures. Hydrous-pyrolysis kinetic parameters are determined in the presence of water at lower temperatures in a closed system, which allows differentiation of bitumen and oil generation, interaction of free-radical initiators, greater radical selectivity, and more distinguishable rate constants as would occur during natural maturation. Kinetic parameters derived from hydrous pyrolysis show good correlations with one another (compensation effect) and kerogen organic-sulfur contents. These correlations allow for indirect determination of hydrous-pyrolysis kinetic parameters on the basis of the organic-sulfur mole fraction of an immature Type-II or -IIS kerogen.     

Alpine reworking of Ordovician protoliths in the Western Carpathians: Geochronological and geochemical data on the Muráñ Gneiss Complex, Slovakia

Magmatic protoliths of Ordovician age have been identified in the metamorphic rocks of the Muráñ Gneiss Complex, Veporic Unit (Central Western Carpathians). Vapor digestion single zircon U–Pb dating yields an intrusion age of 464 ± 35 Ma (upper intercept) for the granite protolith. A lower intercept age of 88 ± 40 Ma records amphibolite-facies metamorphic overprint in the Cretaceous, during the Alpine orogeny. Geochemical and isotopic data suggest crustal origin of the orthogneiss. Nd_initial are between − 2.6 and − 5.0 and T_DM^Nd between 1.3 and 1.5 Ga (two-step approach). ⁸⁷Sr / ⁸⁶Sr_initial ratios vary between 0.7247 and 0.7120, and a steep REE pattern further constrains the crustal affinity of these rocks. Associated amphibolite bodies have Nd_initial values of 6.5, ⁸⁷Sr / ⁸⁶Sr_initial ratio of 0.7017, and a flat REE pattern. They are interpreted as MORB derived metabasites. Whole-rock Pb isotope analyses define a linear array in a ²⁰⁶Pb / ²⁰⁴Pb vs. ²⁰⁷Pb / ²⁰⁴Pb diagram with an age of ca. 134 Ma, consistent with intense Alpine metamorphism and deformation.

These basement rocks of the Central Western Carpathians are interpreted as Ordovician magmatic rocks intruded at an active margin of Gondwana. They represent the eastern prolongation of Cambro–Ordovician units of the European Variscides, which were part of the peri-Gondwana superterrane and accreted to Laurussia during the Variscan orogeny. Variscan metamorphic overprint is not recorded by the isotopic data of the Muráñ Gneiss Complex. Alpine metamorphism is the most dominant overprint.     

Study of geothermal water intrusion due to groundwater exploitation in the Puebla Valley aquifer system, Mexico

Significant intrusion of geothermal water into fresh groundwater takes place in the Puebla Valley aquifer system, Mexico. The decline in the potentiometric surface due to the overexploitation of the groundwater induces this intrusion. This hydrological system comprises three aquifers located in Plio-Quaternary volcanic sediments and Mesozoic calcareous rocks. The hydraulic balance of the aquifer shows that the annual output exceeds the natural inputs by 12 million m³. Between 1973 and 2002, a drop in the potentiometric surface, with an 80 m cone of depression, was identified in a 5-km-wide area located southwest of the city of Puebla. Chemical analyses performed on water samples since 1990 have shown an increase in total dissolved solids (TDS) of more than 500 mg/L, coinciding with the region showing a cone of depression in the potentiometric surface. A three-dimensional flow and transport model, based on the hydrogeological and geophysical studies, was computed by using the MODFLOW and MT3D software. This model reproduces the evolution of the aquifer system during the last 30 years and predicts for 2010 an additional drawdown in the potentiometric surface of 15 m, and an increase in the geothermal water intrusion.     

A Practical Procedure for the Measurement of Fragmentation by Blasting by Image Analysis

Summary. The operation of a digital image analysis system in a limestone quarry is described. The calibration of the system, required in order to obtain moderately reliable fragmentation values, is done from muckpile sieving data by tuning the image analysis software settings so that the fragmentation curve obtained matches as close as possible the sieving. The sieving data have also been used to extend the fragment size distribution curves measured to sizes below the system’s optical resolution and to process the results in terms of fragmented rock, discounting the material coming from a loose overburden (natural fines) that is cast together with the fragmented rock. Automatic and manual operation modes of the image analysis are compared. The total fragmentation of a blast is obtained from the analysis of twenty photographs; a criterion for the elimination of outlier photographs has been adopted using a robust statistic. The limitations of the measurement system due to sampling, image processing and fines corrections are discussed and the errors estimated whenever possible. An analysis of consistency of the results based on the known amount of natural fines is made. Blasts with large differences in the amount of fines require a differentiated treatment, as the fine sizes tend to be the more underestimated in the image analysis as they become more abundant; this has been accomplished by means of a variable fines adjustment factor. Despite of the unavoidable errors and the large dispersion always associated with large-scale rock blasting data, the system is sensitive to relative changes in fragmentation.     

Catastrophic debris flows near Machu Picchu village (Aguas Calientes), Peru

Slope movements together with intensive river erosion and the following accumulation are the leading processes in the landscape evolution in the area of Machu Picchu village (former Aguas Calientes), which is located close to the Machu Picchu Sanctuary. Debris flows affect not only the bottoms of valleys or canyons, but also debris fans at the termini of the drainage basins, which are heavily inhabited at some places. The most recent event in the Machu Picchu village occurred in April 2004, but several others were documented in a broader area in the last 50 years. The field inspections at Machu Picchu (May and September 2004; June and September 2005) together with oral testimony revealed the nature and behavior of the debris flow. Machu Picchu village can be assessed as a zone with high landslide risk in relation to its urban development. Despite that, the village recorded a rapid growth (threefold population increase) without urban control within the past two decades. Precipitation, which is the main triggering factor of the debris flows, and natural hazard management of the Machu Picchu village are discussed in this paper.     

Will the river Irtysh survive the year 2030? Impact of long-term unsuitable land use and water management of the upper stretch of the river catchment (North Kazakhstan)

The Irtysh river basin all the way from river spring in China across Kazakhstan as far as the Russian part of Siberia is among the most ecologically endangered and affected regions on our planet. The study provides a summary of the historical reasons for anthropological interventions in this area, which began with the construction of plants of the military—industrial complexes in the forties of the last century during World War II. These plants have a major share in extreme high concentrations of heavy metals in surface as well in groundwaters locally. The Semipalatinsk nuclear polygon plays a specific role as a source of contamination of local waters. The release of top secret data enabled us to gain knowledge about serious problems related to high radioactivity of groundwaters, which should spread uncontrollably through a system of secondary fissures activated by nuclear blasts. Another serious problem in this region is the quantitative aspect of contamination. Model simulations of water balance indicate that large industrial development in the spring area in China and continuously increasing water consumption in Kazakhstan may lead to desiccation of the lower stretch of this large river in Siberia during the summer months of 2030.     

The Spačice eclogite: constraints on the P–T–t history of the Gföhl granulite terrane, Moldanubian Zone, Bohemian Massif

Summary In the Kutná Hora Complex, the Běstvina Formation, which is similar to Gf?hl granulite, contains eclogite that has escaped widespread retrograde recrystallization. The eclogite assemblage, garnet + omphacite + quartz + rutile ± plagioclase, yields an estimate for peak metamorphic conditions of 18–20 kbar and 835–935 °C, which is comparable to that determined from felsic granulite, 14–20 kbar and 900–1000 °C. Garnet in eclogite exhibits both prograde and retrograde compositional zoning, from which constraints on thermal history of the Gf?hl terrane can be derived by diffusion modelling. At 900 °C, a garnet grain of 800–1000 μm radius would homogenize in 7.5–11.7 million years, but the existence of compositional gradients on a length scale of 100–200 μm suggests that the duration of peak metamorphism may have been limited to ∼500,000 years. Diffusion modelling of retrograde zoning in garnet yields a cooling rate of 150–100 °C/m.y. for a radius of 800–1000 μm and initial temperature of 900 °C. The relatively brief duration of high-pressure/high-temperature metamorphism and rapid cooling and exhumation of the Gf?hl terrane may be a consequence of lithospheric delamination during Early Carboniferous collision of Bohemia (Teplá-Barrandia) and Moldanubia (Franke, 2000).     

Alteration, evaluation and use of extremaduran granite residues

The necessity of eliminating debris from a granite quarry has awakened an interest in applications of by-products, called “marginal arids”, in different fields, like construction and foundations for roadways, restoration, material for the manufacture of artificial rocks, and artesian products etc. Conclusions obtained from the results of tests carried out by X-ray diffraction of granite quarry by-products in Extremadura, Spain, submitted to different treatments, are established. Test pieces from two quarries are analyzed and compared generally and specifically, for commercial use. Finally, conclusions relating to essays in test pieces and mineral dynamics of marginal arid granite are exposed.     

T -distributed Random Fields: A Parametric Model for Heavy-tailedWell-log Data1

Histograms of observations from spatial phenomena are often found to be more heavy-tailed than Gaussian distributions, which makes the Gaussian random field model unsuited. A T-distributed random field model with heavy-tailed marginal probability density functions is defined. The model is a generalization of the familiar Student-T distribution, and it may be given a Bayesian interpretation. The increased variability appears cross-realizations, contrary to in-realizations, since all realizations are Gaussian-like with varying variance between realizations. The T-distributed random field model is analytically tractable and the conditional model is developed, which provides algorithms for conditional simulation and prediction, so-called T-kriging. The model compares favourably with most previously defined random field models. The Gaussian random field model appears as a special, limiting case of the T-distributed random field model. The model is particularly useful whenever multiple, sparsely sampled realizations of the random field are available, and is clearly favourable to the Gaussian model in this case. The properties of the T-distributed random field model is demonstrated on well log observations from the Gullfaks field in the North Sea. The predictions correspond to traditional kriging predictions, while the associated prediction variances are more representative, as they are layer specific and include uncertainty caused by using variance estimates.     

P–T evolution and reaction textures in retrogressed eclogites from Svetlik, the Moldanubian Zone (Czech Republic)

Summary Lenses and pods of mafic rocks from the Monotonous Unit near Svetlik are characterized by eclogite facies mineral assemblages; however some inclusion patterns (oriented quartz rods in clinopyroxene and cuboids of disordered graphite in garnet) that are usually known from ultra-high pressure rocks were also observed in one sample. Conventional thermobarometry yielded maximum P–T conditions of 2.0–2.5 GPa and 750 °C. Decompression and heating at amphibolite and granulite facies conditions resulted in the formation of at least five distinct types of symplectites. These include symplectitic intergrowth of ilmenite and clinopyroxene after titanite, described here for the first time from the Moldanubian Zone. In addition, symplectites of plagioclase and biotite with accessory amounts of spinel after tabular pseudomorphs (after phengite?) are also reported here. Mass balance relations indicate that symplectites of diopside + plagioclase after omphacite and plagioclase + spinel (sapphirine) after kyanite + garnet, formed by nearly isochemical reactions. All other symplectite-forming reactions were allochemical and were accelerated by the presence of fluid in the primary phases. Preserved zoning pattern in garnet with high compositional gradient in some samples suggests that the rocks were affected briefly by granulite facies overprint.