Metamorphic and deformational imprint of Cambrian–Lower Ordovician rifting in the Ossa-Morena Zone (Iberian Massif, Spain)

The high-temperature metamorphism recorded in the Valuengo and Monesterio areas constitutes a rare occurrence in the Ossa-Morena Zone of Southwest Iberia, where low-grade metamorphism dominates. The metamorphism of the Valuengo area has been previously considered either Cadomian or Variscan in age, whereas that of Monesterio has been interpreted as a Cadomian imprint. However, these areas share important metamorphic and structural features that point towards a common tectonometamorphic evolution. The metamorphism of the Valuengo and Monesterio areas affects Late Proterozoic and Early Cambrian rocks, and is syn-kinematic with a top-to-the-north mylonitic foliation, which was subsequently deformed by early Variscan folds and thrusts. The U–Pb zircon age (480±7 Ma) we have obtained for an undeformed granite of the Valuengo area is consistent with our geological observations constraining the age of the metamorphism. We propose that this high-temperature metamorphic imprint along a NW–SE ductile extensional shear zone is related to the crustal extension that occurred in the Ossa-Morena Zone during the Cambro-Ordovician rifting. In the same way, the tectonothermal effect of the preorogenic rifting stage may have been wrongly attributed to orogenic processes in other regions as well as in this one.     

Validation of Landslide Susceptibility Maps; Examples and Applications from a Case Study in Northern Spain

A procedure for validating landslide susceptibility maps wasapplied in a study area in northern Spain and the results obtained compared. Validationwas used to carry out sensitivity analysis for individual variables and combinationsof variables. The validity of different map-making methods was tested, as well as theutility of different types of Favourability Functions. The results obtained show thatvalidation is essential to determine the predictive value of susceptibility maps. Italso helps to better select the most suitable function and significant variables, thus improving the efficiency of the mapping process. Validation based on a temporal strategy makes it possible to derive hazard maps from susceptibility maps.     

Kinetics and Mechanism of Trithionate and Tetrathionate Oxidation at Low pH by Hydroxyl Radicals

The oxidation kinetics of trithionate (S₃O₆^2- ) and tetrathionate (S₄O ₆ ^2- ) with hydroxyl radicals (OH^*) have been investigated in systems analogous to acid mine drainage (AMD) environments. The discovery of hydroxyl radical (OH^*) formation on pyrite surfaces (Borda et al., 2003) suggests hydroxyl radicals may affect the oxidation kinetics of intermediate sulfur species such as tetrathionate. Cyclic voltammetry experiments in acidic solutions indicate that the reaction of S₄O ₆ ^2- with OH^* goes through an unknown intermediate, tentatively assigned as S₃O ₄ ^n- . An outer-sphere electron transfer mechanism for the reaction of S₄O ₆ ^2- with OH^* to form S₃O ₄ ^n- is proposed based on experimental results. Oxidation rates for trithionate and tetrathionate in the presence of Fenton's reagent (which forms hydroxyl radicals) are too fast to be directly measured using UV-Vis spectrophotometry, electrochemical, or stop-flow spectrophotometry methods. Competitive reaction kinetics within the context of the Haber—Weiss mechanism suggests that the rate constant for the oxidation of trithionate and tetrathionate with OH^* is in excess of 10⁸ M^-1 sec^-1.     

Stable isotopes in deep-sea corals and a new mechanism for “vital effects”

Offsets from isotopic equilibrium in biogenic carbonates have complicated paleoclimate reconstructions for decades. A new archive of climate, deep-sea corals, is used to evaluate the calcification processes, independent of photosynthesis, that contribute to these offsets. Carbon and oxygen stable isotope data from six modern deep-sea corals show strong linear trends between δ¹³C and δ¹⁸O. Slopes of these trends between samples are similar and range between 1.9 to 2.6 for Δδ¹³C/Δδ¹⁸O. Linear trends intersect isotopic equilibrium for δ¹⁸O and are slightly depleted for δ¹³C. Variations in the isotopic ratios are strongly correlated with the density banding structure. Isotopically depleted aragonite is associated with light, quickly precipitating bands, whereas isotopically enriched points correspond to slowly accumulating, less dense aragonite. The densest white band at the trabecular center is furthest from isotopic equilibrium for both carbon and oxygen. Data from this region fall off the linear trend between δ¹⁸O and δ¹³C. This deviation, where δ¹³C remains constant while the δ¹⁸O continues to decrease, does not support “vital effect” mechanisms that call upon kinetic fractionation to explain offsets from isotopic equilibrium. We propose a new mechanism for vital effects in these deep-sea corals that is based on a thermodynamic response to a biologically induced pH gradient in the calcifying region.     

Evidence for fullerenes in solid bitumen from pillow lavas of Proterozoic age from Mítov (Bohemian Massif, Czech Republic)

Andesitic pillow lavas containing biogenic, solid bitumen (SB) are a constituent of a Neoproterozoic volcanosedimentary sequence (Teplá-Barrandian unit, Bohemian Massif) in the Mítov area of the Czech Republic. A black shale formation that is crosscut by these andesitic basalts is 565 Ma old. Carbon disulfide extracts of two powdered samples of SB contain 0.2 and 0.3 ppm of C₆₀, respectively, as determined by high-pressure liquid chromatography. The peak assignment based on retention time is fully supported by high-resolution electron ionization mass spectrometry (EI-MS). No C₇₀ was detected, nor was C₆₀ found in two other SB samples from this locality. Other investigated carbonaceous samples from Bohemia (coals and anthracites of Upper Paleozoic age and anthraxolite, graphitoids, and graphite of Upper Proterozoic age) did not contain fullerenes at concentrations above the detection limit of 0.01 ppm. The absence of C₆₀ in these samples was confirmed by EI-MS. The proposed mechanism of fullerene formation involves a primary algal phase, generation of a hydrocarbonaceous mixture in the course of thermal evolution of the sedimentary series, and their high-temperature transformation related to the extrusion of basalt. An important feature for fullerene conservation was the enclosure of fullerenes in SB with a structure similar to glasslike carbon, where the fullerene was protected against oxidation.     

Modelling nitrogen and oxygen isotope fractionation during denitrification in a lacustrine redox-transition zone

The stable isotope composition (δ¹⁵N and δ¹⁸O) of nitrate was measured during Summer 1999 in the anaerobic hypolimnion of eutrophic Lake Lugano (Switzerland). Denitrification was demonstrated by a progressive nitrate depletion coupled to increasing δ¹⁵N and δ¹⁸O values for residual nitrate. Maximum δ¹⁵N and δ¹⁸O values amounted to 27.2 and 15.7‰, respectively.¹⁵N and ¹⁸O enrichment factors for denitrification (ε) were estimated using a closed-system model and a dynamic diffusion-reaction model. Using the Rayleigh equation (closed-system approach), we obtained ε values of −11.2 and −6.6‰ for nitrogen and oxygen, respectively. The average ε values derived using the diffusion-reaction model were determined to be −20.7 ± 3.8 for nitrogen and −11.0 ± 1.7 for oxygen. Both N and O isotope fractionation appeared to be lower when denitrification rates where high, possibly in association with high organic carbon availability. In addition, variations in the isotope effects may be attributed to the variable importance of sedimentary denitrification having only a small isotope effect on the water column. The combined measurement of N and O isotope ratios in nitrate revealed that coupled nitrification-denitrification in the open-water was of minor importance. This is the first study of nitrogen and oxygen isotope effects associated with microbial denitrification in a natural lake. Moreover, this study confirms the high potential of δ¹⁸O of nitrate as a valuable biogeochemical tracer in aquatic systems, complementing nitrate δ¹⁵N.     

The impact of accelerometry on CHAMP orbit determination

 The contribution of the STAR accelerometer to the CHAMP orbit precision is evaluated and quantified by means of the following results: orbital fit to the satellite laser ranging (SLR) observations, GPS reduced-dynamic vs SLR dynamic orbit comparisons, and comparison of the measured to the modeled non-gravitational accelerations (atmospheric drag in particular). In each of the four test periods in 2001, five CHAMP arcs of 2 days' length were analyzed. The mean RMS-of-fit of the SLR observations of the orbits computed with STAR data or the non-gravitational force model were 11 and 24 cm, respectively. If the accelerometer calibration parameters are not known at least at the few percent level, the SLR orbit fit deteriorates. This was tested by applying a 10% error to the along-track scale factor of the accelerometer, which increased the SLR RMS-of-fit on average to 17 cm. Reference orbits were computed employing the reduced-dynamic technique with GPS tracking data. This technique yields the most accurate orbit positions thanks to the estimation of a large number of empirical accelerations, which compensate for dynamic modeling errors. Comparison of the SLR orbits, computed with STAR data or the non-gravitational force model, to the GPS-based orbits showed that the SLR orbits employing accelerometer observations are twice as accurate. Finally, comparison of measured to modeled accelerations showed that the level of geomagnetic activity is highly correlated with the atmospheric drag model error, and that the largest errors occur around the geomagnetic poles. Received: 7 May 2002 / Accepted: 18 November 2002 Correspondence to: S. Bruinsma Acknowledgments. The TIGCM results were obtained from the CEDAR database. This study was supported by the Centre National d'Etudes Spatiales (CNES). The referees are thanked for their helpful remarks and suggestions.     

Regional effects of large-scale extreme wind events over orographically structured terrain

Summary ?Above orographically structured terrain considerable differences of the regional wind field may be identified during large-scale extreme wind events. So far, these regional differences could not be resolved by climate models. To determine the relationships between large-scale atmospheric conditions, the influence of orography, and the regional wind field, data measured in the upper Rhine valley within the framework of the REKLIP Regional Climate Project were analyzed and calculations were made using the KAMM mesoscale model. In the area of the upper Rhine valley, ratios of the wind velocity in the Rhine valley at 10 m above ground level, ν_val, and the large-scale flow velocity, ν_lar, are between ν_val/ν_lar ≈ 0.1 and ν_val/ν_lar ≈ 1. The ν_val/ν_lar ratio exhibits a strong dependence on thermal stratification, δ, and decreases from ν_val/ν_lar ≈ 1 at δ = 0 K m⁻¹ to ν_val/ν_lar ≈ 0.2 at δ = 0.0075 K m⁻¹. In areas, where the lateral mountainous border of the Rhine valley is interrupted, the ν_val/ν_lar ratio increases again with increasing stability or decreasing Froude number. This is obviously due to flow around the Black Forest under stable stratification. It is demonstrated by model calculations that a complex wind field develops in the Rhine valley at small Froude numbers (Fr < 1) irrespective of the direction of large-scale flow. The ν_val/ν_lar ratio is characterized by small values in the direct lee side (ν_val/ν_lar ≈ 0.2) and high values on the windward side of the lateral mountainous border of the Rhine valley (ν_val/ν_lar ≈ 0.8). Received October 22, 2001; revised June 18, 2002; accepted June 23, 2002