Präorogene Versenkungstiefe und Orogenese als Diagenesefaktoren für altpaläozoische Kontinentalrandbildungen der Nördlichen Appalachen in Quebec,Kanada

This paper presents data and preliminary interpretations on the diagenesis of Early Paleozoic continental margin deposits along a traverse of the Quebec Appalachians near Quebec City, Canada. Regional variations in diagenesis were studied using the thermal maturation of organic matter in shales (reflectance measured on asphaltic bitumen, 105 samples) and illite crystallinity (330 samples). These revealed a regional southeastward increase in grade from the late middle and late stage of diagenesis to epimetamorphism, which is reflected in the distinction of four zones: Zone I representing the late middle diagenetic stage has a mean reflectance in oil (R₀) between 1.0 and 1.5% and illite crystallinity between 5.5 and 8.0 mm. Zone II (late diagenetic stage) is characterized by R₀=1.5–2.6% and illite crystallinity between 3.5 and 5.5 mm. Anomalously poor illite crystallinities in Zone II (i. e. 5.5 to 8.0 mm) were obtained for black shales, in which improvement of crystallinity lags behind red and green shales. Zone II is subdivided into subzones IIA and IIB. In the former, reflectance and illite crystallinity increase, within individual nappes, as a function of age or depth of burial. In the latter no such dependence is observed, instead diagenetic grade increases regionally in a southeastward direction as it does in zones III and IV. Zone III represents the anchizone in which observed reflectance values R₀ range from 2.6 to 4.0% and illite crystallinities from 2.0 to 3.1 mm. In Zone IV (epizone) illite crystallinity is less than 2.0 mm (In terms of reflectance the anchi-zone/epizone boundary was not defined). Zones I and IIA are anomalous in that lower tectonic units are diagenetically less altered than higher tectonic units: R₀ varies from 1.71 to 2.30% for the highest tectonic unit (Cambrian Chaudière Nappe), 1.53 to 1.90% (Cambro-Ordovician Bacchus Nappe) and 1.08 to 1.46% (Lower Ordovician Pointe-de-Lévy Nappe) for the middle tectonic units, and 1.01 to 1.15% for the lowest tectonic unit (Middle Ordovician Quebec Promotory Nappe). Thermal maturation and mineral diagenesis in zone IIA are probably due solely to sedimentary burial at the original site of deposition (by an estimated 6 to 7 km of younger sediments) because in this zone the highest diagenetic grade occurs in the highest tectonic unit. Diagenesis in the nappes of zone I probably required additional tectonic burial by the higher nappes because original sedimentary thicknesses that once overlay these Lower and Middle Ordovician rocks appear insufficient to have caused the observed degree of diagenesis. Diagenesis in zone IIA, therefore, was most likely formed entirely before orogenesis; in zone I it is probably partly pre-orogenic in origin and has been transported during nappe-movement. In contrast, diagenesis and metamorphism in zones IIB to IV are interpreted as related to regional synorogenic heating in conjunction with the Taconic orogeny. Thermal maturation levels in zone I indicate that the rocks have not yet passed the “oil window” which is of interest for petroleum exploration in Quebec. An extended English version of this paper is in preparation for the Bulletin of Canadian Petroleum Geology (Ogunyomi et al., ms.).     

The farmer,the worker and the MP

The territorial dimension of the digital divide is usually considered as a phenomenon that penalizes the peripheral regions, especially in terms of regional economic development. Taking into account the territorial networking of ICT (Information & Communication Technologies) infrastructures—particularly high-speed networks—provides what is probably the principal reason for such a perception. This is particularly true considering that the most-peripheral regions and those with the smallest population densities are also the poorest in terms of ICT infrastructures. In Western countries, however, the digital divide is no longer the result of network-related problems. Nowadays, the issue of the skills required to adequately exploit the potential of ICT is at the forefront. Yet this evolution is likely to lead to an inversion of the inequalities between the centre and the periphery, as populations without such skills—recent immigrants, the unemployed, the illiterate, people with little education or on low incomes and other socially marginalized people—are generally concentrated in urban centres. Consequently, the priority for reducing inequalities of access to ICT resources is no longer the provision of high-performance ICT infrastructures for peripheral regions, but rather the implementation of continuing education and social action policies within the urban centres.     

Secondary Ion Mass Spectrometry Bias on Isotope Ratios in Dolomite–Ankerite,Part I: δ18O Matrix Effects

We document the development of a suite of carbonate mineral reference materials for calibrating SIMS determinations of δ¹⁸O in samples with compositions along the dolomite–ankerite solid solution series [CaMg(CO₃)₂–CaFe(CO₃)₂]. Under routine operating conditions for the analysis of carbonates for δ¹⁸O with a CAMECA IMS 1280 instrument (at WiscSIMS, University of Wisconsin‐Madison), the magnitude of instrumental bias along the dolomite–ankerite series decreased exponentially by ~ 10‰ with increasing Fe content in the dolomite structure, but appeared insensitive to minor Mn substitution [< 2.6 mol% Mn/(Ca+Mg+Fe+Mn)]. The compositional dependence of bias (i.e., the sample matrix effect) was calibrated using the Hill equation, which relates bias to the Fe# of dolomite–ankerite [i.e., molar Fe/(Mg+Fe)] for thirteen reference materials (Fe# = 0.004–0.789); for calibrations employing either 10 or 3 μm diameter spot size measurements, this yielded residual values ≤ 0.3–0.4‰ relative to CRM NBS 19 for most reference materials in the suite. Analytical precision was ± 0.3‰ (2s, standard deviations) for 10‐μm spots and ± 0.7‰ (2s) for 3‐μm spots, based on the spot‐to‐spot repeatability of a drift monitor material that ‘bracketed’ each set of ten sample‐spot analyses. Analytical uncertainty for individual sample analyses was approximated by a combination of precision and calibration residual values (propagated in quadrature), suggesting an uncertainty of ± 0.5‰ (2s) for 10‐μm spots and ± 1‰ (2s) for 3‐μm spots.     

Mineralogical and chemical characteristics of some natural jarosites

This paper presents a detailed study of the mineralogical, microscopic, thermal, and spectral characteristics of jarosite and natrojarosite minerals. Systematic mineralogic and chemical examination of a suite of 32 natural stoichiometric jarosite and natrojarosite samples from diverse supergene and hydrothermal environments indicates that there is only limited solid solution between Na and K at low temperatures, which suggests the presence of a solvus in the jarosite-natrojarosite system at temperatures below about 140 °C. The samples examined in this study consist of either end members or coexisting end-member pairs of jarosite and natrojarosite. Quantitative electron-probe microanalysis data for several natural hydrothermal samples show only end-member compositions for individual grains or zones, and no detectable alkali-site deficiencies, which indicates that there is no hydronium substitution within the analytical uncertainty of the method. In addition, there is no evidence of Fe deficiencies in the natural hydrothermal samples. Hydronium-bearing jarosite was detected in only one relatively young supergene sample suggesting that terrestrial hydronium-bearing jarosites generally are unstable over geologic timescales.Unit-cell parameters of the 20 natural stoichiometric jarosites and 12 natural stoichiometric natrojarosites examined in this study have distinct and narrow ranges in the a- and c-cell dimensions. There is no overlap of these parameters at the 1σ level for the two end-member compositions. Several hydrothermal samples consist of fine-scale (2-10 μm) intimate intergrowths of jarosite and natrojarosite, which could have resulted from solid-state diffusion segregation or growth zoning due to variations in the Na/K activity ratio of hydrothermal solutions.     

Contrasting red bed diagenesis: the southern and northern margin of the Central European Basin

We compare the diagenetic evolution of deeply buried Rotliegend (Permian) red bed sandstones at the southern and northern margin of the Central European Basin (CEB) in Germany. Main target is to evaluate the influence of maturation products from hydrocarbon (HC) source rocks during red bed diagenesis. At the southern margin of the CEB, thick coal-bearing Carboniferous source rocks are omnipresent beneath the Rotliegend. They contain dominantly gas-prone terrigenous organic material and some oil source rocks. Hydrocarbons were generated from Late Carboniferous onwards throughout most of basin subsidence. At the northern margin of the CEB, source rocks are almost absent due to deep erosion of Carboniferous rocks and a low TOC of local Lower Carboniferous relics. Early diagenetic processes are comparable at both basin margins. Significant differences in burial diagenetic evolution are spatially correlated to the occurrence of hydrocarbon source rocks. Burial diagenesis at the southern margin of the CEB is characterized especially by bleaching of red beds, major dissolution events, pervasive illite formation, impregnation of pore surfaces with bitumen, and formation of late Fe-rich cements. Almost none of these features were detected at the northern basin margin. Instead, relatively early cements are preserved down to maximum burial depths. This suggests that major diagenetic mineral reactions in deeply buried red bed sandstones are controlled by the presence or absence of maturing hydrocarbon source rocks.     

Thermal microstructural changes of grain-supported limestones

The microstructure of grainstone, grain-supported limestone, samples representing different geographic and stratigraphic intervals in Egypt were examined before and after calcination at 950°C for 0.25, 0.5, 1 and 2?h. The examination utilized are X-ray diffraction (XRD), X-ray fluorescence (XRF), transmitted light microscopy (TLM), scanning electron microscopy (SEM) and X-ray micro tomography (??-CT). Both the free lime content and reactivity of the produced quicklime were measured. The quicklime produced at 950°C for 0.25 and 0.5?h is un-reactive (R_DIN < 10) due to its low content of free lime. However, quicklime produced at 1 and 2?h conditions is highly reactive (R_DIN > 30) with variable reactivity due to the differences in the lime microfabric. The grainstones enriched in nummulites resulted in quicklime of higher reactivity than those dominated by foraminifera, peloids and miliolids. This is mainly attributed to the preservation of the intraparticle pores of the original limestone and the development of pinhole and fracture micropores. The shape of pores and not their amount is the main controlling variable in the quicklime reactivity. The grainstones enriched in fracture pores showed more reactive lime, whereas those with compact structures are less reactive post calcination.     

Quantum mechanical calculations of the vibrational spectra of quartz- and rutile-type GeO2

Heat-treatment and stepwise cooling of as-delivered, water-containing quartz-type GeO₂ powder resulted in transformation into a water-free form. A rutile-type modification could be prepared by impregnation of the quartz-type phase with RbOH solutions, drying and annealing. Raman- and FTIR-absorption spectra of quartz- and rutile-type GeO₂ were measured and compared to quantum-mechanical ab initio calculations based on a hybrid functional using the Perdew–Burke–Ernzerhof correlation functional with 16.7% Hartree–Fock exchange density functional. Maximum and mean deviations between measured spectral bands and assigned vibrational modes are 14 and ±8 cm⁻¹ for the quartz-type and 30 and ±13 cm⁻¹ for the rutile-type polymorphic form. Water is incorporated into GeO₄ entities of quartz-type GeO₂; a water-free and structurally stable form can be prepared by a heating up to 1,425 K, tempering at 1,323 K and stepwise cooling. Spectral bands not explained by the calculations suggest defects and distortions in both quartz- and rutile-type structures, in case of the quartz-type one by incomplete transformation into an ideal structure after removing the water, whereas the rutile-type modification most probably incorporates Rb during its synthesis.     

An analysis of the salt water inflow into the Baltic in 1975 to 1976

Time series measurements from light vessel and coastal stations in the transition area of the Kattegat and the Baltic Sea are analyzed for the period August 1975 to March 1976. The data consist of daily sampled salinities from different depth levels and daily means of sea levels, surface current, and wind, respectively. The purpose of this paper is to examine the dynamics of the mass- and salt-transport during a major salt water inflow.The principal conclusions of this paper are that

Subduction of continental margins and the uplift of high-pressure metamorphic rocks

The mechanism by which high-pressure metamorphosed continental material is emplaced at high structural levels is a major unsolved problem of collisional orogenesis. We suggest that the emplacement results from partial subduction of the continental margin which, because of its high flexural rigidity, produces a rapid change in the trajectory of the descending slab. We assume a two-fold increase in effective elastic thickness of the lithosphere as the continental margin approaches the subduction zone, and calculate the flexural profile of a thin plate for progressive downward migration of the zone of increased rigidity. We assess the effect of changes in the flexural profile on the overlying accretionary prism and mantle wedge as the continent approaches by estimating the extra stresses that are imposed on the wedge due to the bending moment exerted by the continental part of the plate. The wedges overlying the subduction zones, and the subducting slab itself, experience substantial extra compressional stress at depths of around 100 km, and extensional stress at shallower depths, as the continental margin passes through the zone of maximum curvature. The magnitudes of such extra stresses are probably adequate to effect significant deformation of the wedge and/or the descending plate, and are experienced in a time interval of less than 5 m.y. for typical subduction rates. The spatial variation of yield stresses in the region of the wedge and descending slab indicates that much of this deformation may be taken up in the crustal part of the descending slab, which is the weakest region in the deeper parts of the subduction zone. This may result in rapid upward migration of the crust of the partially subducted continental margin, against the flow of subduction. High-pressure metamorphosed terranes emplaced by the mechanism envisaged in this paper would be bounded by thrust faults below and normal faults above. Movement on the faults would have been coeval, and would have resulted in rapid unroofing of the high-pressure terranes, synchronous with arrival of the continental margin at the subduction zone and, therefore, relatively early in the history of a collisional orogen.     

The early instrumental warm-bias: a solution for long central European temperature series 1760–2007

Instrumental temperature recording in the Greater Alpine Region (GAR) began in the year 1760. Prior to the 1850–1870 period, after which screens of different types protected the instruments, thermometers were insufficiently sheltered from direct sunlight so were normally placed on north-facing walls or windows. It is likely that temperatures recorded in the summer half of the year were biased warm and those in the winter half biased cold, with the summer effect dominating. Because the changeover to screens often occurred at similar times, often coincident with the formation of National Meteorological Services (NMSs) in the GAR, it has been difficult to determine the scale of the problem, as all neighbour sites were likely to be similarly affected. This paper uses simultaneous measurements taken for eight recent years at the old and modern site at Kremsmünster, Austria to assess the issue. The temperature differences between the two locations (screened and unscreened) have caused a change in the diurnal cycle, which depends on the time of year. Starting from this specific empirical evidence from the only still existing and active early instrumental measuring site in the region, we developed three correction models for orientations NW through N to NE. Using the orientation angle of the buildings derived from metadata in the station histories of the other early instrumental sites in the region (sites across the GAR in the range from NE to NW) different adjustments to the diurnal cycle are developed for each location. The effect on the 32 sites across the GAR varies due to different formulae being used by NMSs to calculate monthly means from the two or more observations made at each site each day. These formulae also vary with time, so considerable amounts of additional metadata have had to be collected to apply the adjustments across the whole network. Overall, the results indicate that summer (April to September) average temperatures are cooled by about 0.4°C before 1850, with winters (October to March) staying much the same. The effects on monthly temperature averages are largest in June (a cooling from 0.21° to 0.93°C, depending on location) to a slight warming (up to 0.3°C) at some sites in February. In addition to revising the temperature evolution during the past centuries, the results have important implications for the calibration of proxy climatic data in the region (such as tree ring indices and documentary data such as grape harvest dates). A difference series across the 32 sites in the GAR indicates that summers since 1760 have warmed by about 1°C less than winters.