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Towards the goal to understand the role of land-surface processes over the Indian sub-continent, a series of soil-moisture sensitivity simulations have been performed using a non-hydrostatic regional climate model COSMO-CLM. The experiments were driven by the lateral boundary conditions provided by the ERA-Interim (ECMWF) reanalysis. The simulation results show that the pre-monsoonal soil moisture has a significant influence on the monsoonal precipitation. Both, positive and negative soil-moisture precipitation (S-P) feedback processes are of importance. The negative S-P feedback process is especially influential in the western and the northern parts of India.
The metasomatised continental mantle may play a key role in the generation of some ore deposits, in particular mineral systems enriched in platinum-group elements (PGE) and Au. The cratonic lithosphere is the longest-lived potential source for these elements, but the processes that facilitate their pre-concentration in the mantle and their later remobilisation to the crust are not yet well-established. Here, we report new results on the petrography, major-element, and siderophile- and chalcophile-element composition of native Ni, base metal sulphides (BMS), and spinels in a suite of well-characterised, highly metasomatised and weakly serpentinised peridotite xenoliths from the Bultfontein kimberlite in the Kaapvaal Craton, and integrate these data with published analyses. Pentlandite in polymict breccias (failed kimberlite intrusions at mantle depth) has lower trace-element contents (e.g., median total PGE 0.72 ppm) than pentlandite in phlogopite peridotites and Mica-Amphibole-Rutile-Ilmenite-Diopside (MARID) rocks (median 1.6 ppm). Spinel is an insignificant host for all elements except Zn, and BMS and native Ni account for typically <25% of the bulk-rock PGE and Au. High bulk-rock Te/S suggest a role for PGE-bearing tellurides, which, along with other compounds of metasomatic origin, may host the missing As, Ag, Cd, Sb, Te and, in part, Bi that are unaccounted for by the main assemblage.
The close spatial relationship between BMS and metasomatic minerals (e.g., phlogopite, ilmenite) indicates that the lithospheric mantle beneath Bultfontein was resulphidised by metasomatism after initial melt depletion during stabilisation of the cratonic lithosphere. Newly-formed BMS are markedly PGE-poor, as total PGE contents are <4.2 ppm in pentlandite from seven samples, compared to >26 ppm in BMS in other peridotite xenoliths from the Kaapvaal craton. This represents a strong dilution of the original PGE abundances at the mineral scale, perhaps starting from precursor PGE alloy and small volumes of residual BMS. The latter may have been the precursor to native Ni, which occurs in an unusual Ni-enriched zone in a harzburgite and displays strongly variable, but overall high PGE abundances (up to 81 ppm). In strongly metasomatised peridotites, Au is enriched relative to Pd, and was probably added along with S. A combination of net introduction of S, Au +/− PGE from the asthenosphere and intra-lithospheric redistribution, in part sourced from subducted materials, during metasomatic events may have led to sulphide precipitation at ~80–120 km beneath Bultfontein. This process locally enhanced the metallogenic fertility of this lithospheric reservoir. Further mobilisation of the metal budget stored in these S-rich domains and upwards transport into the crust may require interaction with sulphide-undersaturated melts that can dissolve sulphides along with the metals they store.
Abstract
The mineralogy, chemical composition, and physical properties of cratonic mantle eclogites with oceanic crustal protoliths can be modified by secondary processes involving interaction with fluids and melts, generated in various slab lithologies upon subduction (auto‐metasomatism) or mantle metasomatism after emplacement into the cratonic lithosphere. Here we combine new and published data to isolate these signatures and evaluate their effects on the chemical and physical properties of eclogite. Mantle metasomatism involving kimberlite‐like, ultramafic carbonated melts (UM carbonated melts) is ubiquitous though not pervasive, and affected between ~20% and 40% of the eclogite population at the various localities investigated here, predominantly at ~60–150 km depth, overlapping cratonic midlithospheric seismic discontinuities. Its hallmarks include lower jadeite component in clinopyroxene and grossular component in garnet, an increase in bulk‐rock MgO ± SiO2, and decrease in FeO and Al2O3 contents, and LREE‐enrichment accompanied by higher Sr, Pb, Th, U, and in part Zr and Nb, as well as lower Li, Cu ± Zn. This is mediated by addition of a high‐temperature pyroxene from a UM carbonated melt, followed by redistribution of this component into garnet and clinopyroxene. As clinopyroxene‐garnet trace‐element distribution coefficients increase with decreasing garnet grossular component, clinopyroxene is the main carrier of the metasomatic signatures. UM carbonated melt‐metasomatism at >130–150 km has destroyed the diamond inventory at some localities. These mineralogical and chemical changes contribute to low densities, with implications for eclogite gravitational stability, but negligible changes in shear‐wave velocities, and, if accompanied by H2O‐enrichment, will enhance electrical conductivities compared to unenriched eclogites.
Plain Language Summary
Oceanic crust formed at spreading ridges is recycled in subduction zones and undergoes metamorphism to eclogite. Some of this material is captured in the overlying lithospheric mantle, where it is exhumed by passing magmas. Having formed in spreading ridges, these eclogites have proven invaluable archives for the onset of plate tectonics, for the construction of cratons during subduction/collision, as probes of the convecting mantle from which their precursors formed, and as generators of heterogeneity upon recycling into Earth's convecting mantle. During subduction and until exhumation, interaction with fluids and melts (called metasomatism) can change the mineralogy, chemical composition, and physical properties of mantle eclogites, complicating their interpretation, but a comprehensive study of these effects is lacking so far. We investigated mantle eclogites from ancient continents (cratons) around the globe in order to define hallmarks of metasomatism by subduction‐related fluids and small‐volume ultramafic carbonated mantle melts. We find that the latter is pervasive and occurs predominantly at midlithospheric depths where seismic discontinuities are detected, typically causing diamond destruction and a reduction in density. This has consequences for their gravitational stability and for the interpretation of shearwave velocities in cratons.
Cratonic eclogite is the product of oceanic crust subduction into the subcontinental lithospheric mantle, and it also is a fertile diamond source rock. In contrast to matrix minerals in magma-borne xenoliths, inclusions in diamond are shielded from external fluids, retaining more pristine information on the state of the eclogite source at the time of encapsulation. Vanadium is a multi-valent element and a widely used elemental redox proxy. Here, we show that that xenolithic garnet has lower average V abundances than garnet inclusions. This partly reflects crystal-chemical controls, whereby higher average temperatures recorded by inclusions, accompanied by enhanced Na2O and TiO2 partitioning into garnet, facilitate V incorporation at the expense of clinopyroxene. Unexpectedly, although diamond formation is strongly linked to metasomatism and xenoliths remained open systems, V concentrations are similar for bulk eclogites reconstructed from inclusions and from xenoliths. This suggests an oxygen-conserving mechanism for eclogitic diamond formation, and implies that eclogite is an efficient system to buffer fO2 over aeons of lithospheric mantle modification by subduction-derived and other fluids.
Chemical reduction-oxidation mechanisms within mantle rocks link to the terrestrial carbon cycle by influencing the depth at which magmas can form, their composition, and ultimately the chemistry of gases released into the atmosphere. The oxidation state of the uppermost mantle has been widely accepted to be unchanged over the past 3800 m.y., based on the abundance of redox-sensitive elements in greenstone belt–associated samples of different ages. However, the redox signal in those rocks may have been obscured by their complex origins and emplacement on continental margins. In contrast, the source and processes occurring during decompression melting at spreading ridges are relatively well constrained. We retrieve primary redox conditions from metamorphosed mid-oceanic ridge basalts (MORBs) and picrites of various ages (ca. 3000–550 Ma), using V/Sc as a broad redox proxy. Average V/Sc values for Proterozoic suites (7.0 ± 1.4, 2σ, n = 6) are similar to those of modern MORB (6.8 ± 1.6), whereas Archean suites have lower V/Sc (5.2 ± 0.4, n = 5). The lower Archean V/Sc is interpreted to reflect both deeper melt extraction from the uppermost mantle, which becomes more reduced with depth, and an intrinsically lower redox state. The pressure-corrected oxygen fugacity (expressed relative to the fayalite-magnetite-quartz buffer, ΔFMQ, at 1 GPa) of Archean sample suites (ΔFMQ –1.19 ± 0.33, 2σ) is significantly lower than that of post-Archean sample suites, including MORB (ΔFMQ –0.26 ± 0.44). Our results imply that the reducing Archean atmosphere was in equilibrium with Earth’s mantle, and further suggest that magmatic gases crossed the threshold that allowed a build-up in atmospheric O2 levels ca. 3000 Ma, accompanied by the first “whiffs” of oxygen in sediments of that age.
The Alborz Mountains are forming a ~100 km wide, E-W trending mountain chain where individual summits are up to 5000 m in elevation. The Alborz Mountains range are part of the Alpine orogen and are straddling a 2000 km wide area S of the Caspian Sea. The rocks of the Alborz Mountains consist of Neogen sediments, which are affected by folding and faulting. In the western part of the Alborz Mountains the folds and faults are trending NW-SE, whereas in the eastern part they are trending NE-SW. GPS data confirm N-S shortening including dextral strike-slip along ESE-WNW trending faults, and sinistral strike-slip along ENE-WSW trending faults. The present thesis is focusing on the active Garmsar salt nappe, the fragmented roof of which is pierced by rock salt which extruded near the front of the Alborz Mountains Range. During the past 5 m.y. the front of the Alborz chain migrated towards SSW on top of the salt of the Garmsar basin. The salt was squeezed towards SSW and took place at the Great Kavir. The extruded salt is forming the Eyvanekey plateau between the cities of Eyvanekey and Garmsar. Both the Garmsar salt nappe and the Eyvanekey plateau are dextrally displaced for ca. 9 km along the Zirab-Garmsar fault. Structural analyses of the Garmsar salt nappe indicate three different groups of joints which are trending perpendicular and parallel to the local mechanical anisotropy. The folds of the study area are congruent (type 2 and 3 after Ramsay) resulting from viscose inhomogeneous flow. InSAR-Investigations suggest the Alborz Mountains to be lifted up by ca. 1 cm/a, while horizontal shortening is active at a rate of 8 ±2 mm/a. These values are consistent with GPS data. Based on nine „Advanced Synthetic Aperture Radar“ (ASAR) scenarios, produced by the ENVISAT satellite of the European space agency between 2003 and 2006, we used interferograms to map the displacement via 22 increments during 2 – 18 months. The results suggest that the topographic height of the surface of the salt is changing at a rate which is controlled by the season. The displacement ranges from subsidence at -40 to -50 mm/a to uplift of 20 mm/a. In order to investigate the time-dependent deformation with high spatial resolution, we used algorithms which are based on data of small base lines (SBAS). The resulting interferometric SAR time series analyses also suggest that the study area is largely subsiding at a rate that is controlled by the seasons. The map with the averaged LOS deformation velocities, on the other hand, suggests the subsidence to increase from the upper part of the salt nappe towards deeper topographic 5 levels of the agricultural lowlands. The major part of subsidence is probably caused by the annual rainfall which results in subrosion of salt. The spatial changes in the subsidence rate are probably controlled by the distribution of fountains, mining activity at the margin of the salt glacier, and faults and fractures inside the salt. Striking seasonal imprints are obvious along the agricultural areas which are surrounding the Garmsar salt nappe. These areas are rapidly subsiding in summer and spring when groundwater is used for irrigations. The maximum rate of subsidence (40-50 mm/a) is located E and W of the Eyvanekey plateau, where large areas are irrigated. The maximum displacement is 20 mm/a in the farmland and 5 mm/a in the center of the salt nappe. Depth estimates using Euler deconvolution method for gravimetric and magnetic data suggest the salt to extrude from a depth less than ca. 2000 m. The gravity field of the study area is characterized by strong anomalies in the SW and weak anomalies in the NE. A considerable negative anomaly in the N indicates that the northern part subsided, whereas the southern part was lifted up. The seismic data show three major horizons inside the Miocene sediments: the Lower Red Formation, the Qom Formation, and the Upper Red Formation. The western part of the study area seems to be free from salt domes. The layers of the upper part of the Qom Formation show thinning along the NE and NW trending faults. In some areas the seismic reflectors indicate steep faults close the saddle of the folds. NE-SW-, NW-SE and E-Wtrending faults prevail. Analogue experiments have been carried out to extend our knowledge about the evolution of the Garmsar salt dome. We used a scaled model (34 cm * 25 cm * 2.5 cm) that was shortened perpendicular to its long side. The wedge shape of the Alborz Mountains was simulated by a wedge consisting of Styrofoam. Rock salt was simulated using Polydimethylsiloxan (PDMS), a linear viscous material with a viscosity of 2.3*104 Pa s and a density of 0.96 g/cm3 at room temperature. Other sediments were modeled using dry quartz sand. The experimental results can be used to simulate the structural evolution of the study area: The Alborz deformation front was emplaced on top of the salt rocks in the Garmsar area while migrating towards SSW. A salt basin and a salt extrusion have also been produced in the model. Cross sections through the wedge shaped analogue model indicate N- and S-dipping reverse faults, which are in line with the wedge shape of the Alborz chain. Moreover, ENE-WSW trending sinistral and ESE-WNW trending dextral strike-slip faults led to N-S shortening during the Miocene. Structural marker horizons, 6 which have been turned into Z-folds on the western fold limbs and to S-folds on the eastern fold limbs, are comparable with the folds of the study area. Solving the problem of waste is one of the central tasks of environmental protection. It is becoming increasingly difficult to find suitable sites that are acceptable to the public. Salt and salt formations have relevant properties to be utilizing as a repository for each kind of waste. The favorable properties make rock salt highly suitable as a host rock, in particular for nonradioactive and radioactive wastes. The Qom and Garmsar basins are the nearest salt diapirs to the Tehran province, and there are suitable repositories for waste disposal. Based on surface and subsurface data, the Garmsar salt diapir has been investigated as a case example for its suitability as a host and repository for various types of waste. The data used are based on field studies, interferometry, and geophysical investigations. The results of this study suggest the deep bedded salt of the Garmsar Salt Basin to be an appropriate host for the deposition of industrial waste. Rock salt of surficial layers or domes, on the other hand, is not regarded as an appropriate candidate for waste disposal.
During my PhD, I was applying the clumped isotope technique to modern brachiopods and fossil belemnites, and I conducted methodological work. Carbonate clumped isotope thermometry is a tool to reconstruct carbonate precipitation temperatures. In contrast to oxygen isotope thermometry, i.e., the δ18O-thermometer, the carbonate clumped isotope thermometer does not require an estimate for the oxygen isotope composition of the seawater, as it considers the fractionation of isotopes exclusively amongst carbonate isotopologues. The ∆47 value of a carbonate expresses the abundance of the 13C–18O bond bearing carbonate isotopologue, within the carbonate, relative to its random distribution. In thermodynamic equilibrium, the ∆47 value of a given carbonate is solely a function of the carbonate precipitation temperature. However, kinetic isotope fractionations, i.e., vital effects, driven by diffusion, pH or incomplete oxygen isotope exchange between water and dissolved inorganic carbonate species can cause the carbonate to be precipitated with isotopic compositions that are offset from those predicted for thermodynamic equilibrium.
Brachiopods serve as important geochemical archives of past climate conditions. To investigate the nature and significance of kinetic controls on brachiopod shell δ18O and ∆47 values, in collaboration with the BASE-LiNE Earth ITN, I analysed the bulk and clumped isotope compositions of eighteen modern brachiopod shells, collected from different geographic locations and water depths that cover a substantial range of growth temperatures. Growth temperatures and seawater δ18O values for each brachiopod were independently determined. Most of the analysed brachiopods exhibit combined offsets from clumped and oxygen isotope equilibrium, and there is a significant negative correlation between the offset values. The observed correlation slope between offset ∆47 and offset δ18O point to the importance of kinetic effects associated with Knudsen diffusion and incomplete hydration and hydroxylation of CO2 (aq), occurring during biomineralisation. The correlations between the growth rates of the analysed brachiopods and both the offset ∆47 and the offset δ18O values provide further arguments for the presence of kinetic effects. In conclusion, the oxygen and clumped isotope composition of modern brachiopod shells are affected by growth rate-induced kinetic effects that hinder their use for palaeoceanography.
Abstract: Subaqueous carbonates from the Devils Hole caves (southwestern USA) provide a continuous Holocene to Pleistocene North American paleoclimate record. The accuracy of this record relies on two assumptions: That carbonates precipitated close to isotope equilibrium and that groundwater temperature did not change significantly in the last 570 thousand years. Here, we investigate these assumptions using dual clumped isotope thermometry. This method relies on simultaneous analyses of carbonate ∆47 and ∆48 values and provides information on the existence and extent of kinetic isotope fractionation. Our results confirm the hypothesis that calcite precipitation occurred close to oxygen and clumped isotope equilibrium during the last half million years in Devils Hole. In addition, we provide evidence that aquifer temperatures varied by less than ±1°C during this interval. Thus, the Devils Hole calcite δ18O time series exclusively represents changes in groundwater δ18O values. Plain Language Summary: The oxygen isotope composition of cave carbonates records changes in Earth's climate. However, the reliability of such records depends on how stable the carbonate precipitation environment was. Here, we use a novel method called dual clumped isotope thermometry that can provide simultaneous information on a carbonate's growth temperature and whether any additional fractionation processes affected its oxygen and clumped isotope signatures. Specifically, we investigated the Devils Hole caves, which provide a reference oxygen isotope time series for North America. We find that groundwater temperature did not change significantly in the last half-million years. Variations in the oxygen isotope composition of the deposited carbonates solely reflect variations in the oxygen isotope composition of the groundwater.
Brachiopod shells are the most widely used geological archive for the reconstruction of the temperature and the oxygen isotope composition of Phanerozoic seawater. However, it is not conclusive whether brachiopods precipitate their shells in thermodynamic equilibrium. In this study, we investigated the potential impact of kinetic controls on the isotope composition of modern brachiopods by measuring the oxygen and clumped isotope compositions of their shells. Our results show that clumped and oxygen isotope compositions depart from thermodynamic equilibrium due to growth rate-induced kinetic effects. These departures are in line with incomplete hydration and hydroxylation of dissolved CO2. These findings imply that the determination of taxon-specific growth rates alongside clumped and bulk oxygen isotope analyses is essential to ensure accurate estimates of past ocean temperatures and seawater oxygen isotope compositions from brachiopods.
Evidence of hydrothermal activity is reported for the Mesozoic pre- and syn-rift successions of the western Adriatic palaeomargin of the Alpine Tethys, preserved in the Western Southalpine Domain (NW Italy). The products of hydrothermal processes are represented by vein and breccia cements, as well as dolomitization and silicification of the host rocks. In the eastern part of the study area, interpreted as part of the necking zone of the continental margin, Middle Triassic dolostones and Lower Jurassic sediments are crossed by veins and hydrofracturing breccias cemented by saddle dolomite. The precipitation of dolomite cements occurred within the stratigraphic succession close to the sediment–water interface. Despite the shallow burial depth, fluid inclusion microthermometry and clumped isotopes show that hydrothermal fluids were relatively hot (80–150°C). In the western part of the study area, interpreted as part of the hyperextended distal zone, a polyphase history of host-rock fracturing is recorded, with at least two generations of veins cemented by calcite, dolomite and quartz. Vein opening and cementation occurred at shallow burial depth around the time of deposition of the syn-rift clastic succession. Fluid inclusion microthermometry on both quartz and dolomite cements indicates a fluid temperature of 90–130°C, again pointing to hydrothermal fluids. Both in Fenera-Sostegno and Montalto Dora areas, O, C and Sr isotope values, coupled with fluid inclusion and clumped isotope data, indicate that hydrothermal fluids derived from seawater interacted with crustal rocks during hydrothermal circulation. Stratigraphic and petrographic evidence, and U–Pb dating of dolomitized clasts within syn-rift sediments, document that hydrothermal fluids circulated through sediments from the latest Triassic to the Toarcian, corresponding to the entire syn-rift evolution of the western portion of the Adriatic palaeomargin. The documented hydrothermal processes are temporally correlated with regional-scale thermal events that took place in the same time interval at deeper crustal levels.