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Im Lößprofil der Ziegelei Glos bei Lisieux ist eine Abfolge fossiler Boden aufgeschlossen, die sich gut mit der hessischen Lößstratigraphie verbinden läßt. Über dem letztinterglazialen Boden liegen nach einer Diskordanz der Lohner Boden, der E1-, der E2- und der E4-Naß-boden. Letzterer wird häufig als Äquivalent des „Sol de Kesselt" angesehen. Somit zeigt sich auch für dieses Gebiet, daß dieser Boden stratigraphisch nicht dem Lohner Boden entsprechen kann.
Un tuf volcanique a ete mis en evidence dans trois profils de loess de Hesbaye (Rocourt et Lixhe) et du Limbourg neerlandais (Nagelbeek). Ce tuf correspond probablement ä l'Eltviller Tuff connu en Hesse (SEMMEL 1967). En consequence, cette decouverte permet de comparer directement une partie de la sequence des loess du Pleistocene superieur propre ä chaque region
In der Monte Cavallo-Gruppe fand Verf. in Stauseesedimenten fossile Holzstücke, für die die 14 C-Datierung ein Alter von 29 350 ± 460 Jahren vor 1950 n. Chr. ergab. Die schluffigen Ablagerungen, die in etwa 900 m, fast 80 m über dem heutigen Flußbett des T. Caltea aufgeschlossen sind, ruhen auf Schottern und werden von Moräne überlagert.
Aufgrund seiner stratigraphischen Lage und seines 14C-datierten Alters kann das Holz (Picea abies bzw. Larix) einem zeitlichen Äquivalent des Paudorf-Interstadials zugeordnet werden. Dieser Fund von Großresten ermöglicht somit eine erste absolute Datierung des Paudorf-Interstadials für die Südalpen und Oberitalien.
Das Cranium eines fossilen Hominiden des Formenkreises Homo sapiens sapiens wurde relativ-geologisch sowie absolut durch Radiokohlenstoff und Aminosäuren auf ungefähr 31 000 Jahre B.P. datiert. Andere absolute sowie relative Daten an Mollusken und Mammutzähnen in überlagernden jüngeren Straten datieren auf 18 000 — 21000 und 16 000 Jahren B.P. Geomorphologische und geophysikalische Datierungen stimmen somit gut überein. Er ist der älteste datierte und früheste Bewohner Zentraleuropas, der dem Homo sapiens sapiens angehört.
Aus Franken wird die Entwicklung quartärer Hohlformen beschrieben, deren Rekonstruktion mit Hilfe lößstratigraphischer Methoden (fossile Böden, Tuffbänder, Umlagerungszonen etc.) möglich ist. Bei vielen Formen zeigt sich, daß sie bereits größere Vorläuferformen präwürmzeitlichen Alters hatten. Die Entwicklung während des Würms läßt sich an manchen Beispielen in besonders instruktiver Weise verfolgen. Zu Beginn des Würms, im unteren Mittelwürm und im unteren Jungwürm dominierte zeitweise die Abtragung und Verlagerung. Im oberen Mittelwürm sowie im oberen Jungwürm herrschte äolische Lößsedimentation vor. Diese Ergebnisse stimmen gut mit den bereits aus anderen mitteleuropäischen Lößgebieten bekannten Befunden überein. Mit dem Trockental-System von Helmstadt wird die Entwicklung von Hohlformen beschrieben, deren Anlage bis in das ältere Pleistozän zurückreicht.
In vorliegender Untersuchung wurde der Rißlöß zwischen der 1. und 2. fossilen Parabraunerde anhand schwächerer Bodenbildungen und eingeschalteter Abtragungsphasen zu gliedern versucht. Im jüngeren Riß herrschte starke Lößsedimentation vor, wobei es in mindestens 6 kaltfeuchten Abschnitten zur Ausbildung schwacher periglazialer Naßböden kam. Die Naßbodenserie wurde als Bruchköbeler Böden (B) bezeichnet. Im jüngsten Rißlöß ist wenige dm unter dem Eemboden als tephrochronologischer Leithorizont der Krifteler Tuff (vgl. SEMMEL 1968) eingeschaltet. Den mittleren Profilbereich im Rißlöß zeichnen feuchtere Klimaabschnitte mit starken Verschwemmungsphasen aus, die in den meisten Profilen zu erheblichen Diskordanzen geführt haben. An der Basis der wenigen kompletten Rißlöß-Profile treten vorwiegend in Hessen über der zumeist gekappten 2. fossilen Parabraunerde maximal zwei Schwarzerden auf, die von SEMMEL (1968) als Weilbacher Humuszonen bezeichnet werden. Unmittelbar über diesen Schwarzerden folgt die Ostheimer Zone, eine Fließerde aus aufgearbeitetem Solumaterial der liegenden Böden. Insgesamt zeigt die aus den Rißböden rekonstruierte Klimaabfolge — neben geringfügigen Abweichungen — überraschende Parallelen zur paläopedologisch-klimatischen Gliederung der Würmkaltzeit.
Crustal structure at the western end of the North Anatolian Fault Zone from deep seismic sounding
(2001)
The first deep seismic sounding experiment in Northwestern Anatolia was carried out in October 1991 as part of the "German - Turkish Project on Earthquake Prediction Research" in the Mudurnu area of the North Anatolian Fault Zone. The experiment was a joint enterprise by the Institute of Meteorology and Geophysics of Frankfurt University, the Earthquake Research Institute (ERI) in Ankara, and the Turkish Oil Company (TPAO). Two orthogonal profiles, each 120 km in length with a crossing point near Akyazi, were covered in succession by 30 short period tape recording seismograph stations with 2 km station spacing. 12 shots, with charge sizes between 100 and 250 kg, were fired and 342 seismograms out of 360 were used for evaluation. By coincidence an M b = 4.5 earthquake located below Imroz Island was also recorded and provided additional information on Moho and the sub-Moho velocity. A ray tracing method orginally developed by Weber (1986) was used for travel time inversion. From a compilation of all data two generalized crustal models were derived, one with velocity gradients within the layers and one with constant layer velocities. The latter consists of a sediment cover of about 2 km with V p » 3.6 km/s, an upper crystalline crust down to 13 km with V p » 5.9 km/s, a middle crust down to 25 km depth with V p » 6.5 km/s, a lower crust down to 39 km Moho depth with V p » 7.0 km/s and V p » 8.05 km/s below the Moho. The structure of the individual profiles differs slightly. The thickest sediment cover is reached in the Izmit-Sapanca-trough and in the Akyazi basin. Of particular interest is a step of about 4 km in the lower crust near Lake Sapanca and probably an even larger one in the Moho (derived from the Imroz earthquake data). After the catastrophic earthquake of Izmit on 17 August 1999 this significant heterogeneity in crustal structure appears in a new light with regard to the possible cause of the Izmit earthquake. Heterogeneities in structure are frequently also heterogeneities in strength and stress that impede or even lock rupture. The Izmit earthquake is discussed in relation to a large stepover or jog at the North Anatolian Fault.
Aim: Predicting future changes in species richness in response to climate change is one of the key challenges in biogeography and conservation ecology. Stacked species distribution models (S‐SDMs) are a commonly used tool to predict current and future species richness. Macroecological models (MEMs), regression models with species richness as response variable, are a less computationally intensive alternative to S‐SDMs. Here, we aim to compare the results of two model types (S‐SDMS and MEMs), for the first time for more than 14,000 species across multiple taxa globally, and to trace the uncertainty in future predictions back to the input data and modelling approach used.
Location: Global land, excluding Antarctica.
Taxon: Amphibians, birds and mammals.
Methods: We fitted S‐SDMs and MEMs using a consistent set of bioclimatic variables and model algorithms and conducted species richness predictions under current and future conditions. For the latter, we used four general circulation models (GCMs) under two representative concentration pathways (RCP2.6 and RCP6.0). Predicted species richness was compared between S‐SDMs and MEMs and for current conditions also to extent‐of‐occurrence (EOO) species richness patterns. For future predictions, we quantified the variance in predicted species richness patterns explained by the choice of model type, model algorithm and GCM using hierarchical cluster analysis and variance partitioning.
Results: Under current conditions, species richness predictions from MEMs and S‐SDMs were strongly correlated with EOO‐based species richness. However, both model types over‐predicted areas with low and under‐predicted areas with high species richness. Outputs from MEMs and S‐SDMs were also highly correlated among each other under current and future conditions. The variance between future predictions was mostly explained by model type.
Main conclusions: Both model types were able to reproduce EOO‐based patterns in global terrestrial vertebrate richness, but produce less collinear predictions of future species richness. Model type by far contributes to most of the variation in the different future species richness predictions, indicating that the two model types should not be used interchangeably. Nevertheless, both model types have their justification, as MEMs can also include species with a restricted range, whereas S‐SDMs are useful for looking at potential species‐specific responses.
This study reports and discusses new radiometric ages, petrographical and volcanological observations and whole rock geochemical data of the rocks of the Rudnik Mts. volcano-intrusive complex. The complex hosts a Pb-Zn-Ag deposit and belongs to the Serbo-Macedonian metallogenetic belt. Two distinct igneous events are distignuished. The first occurred >30 Ma and was mainly characterized by extrusive and shallow intrusive dacites and andesites and was unrelated to mineralization. The second igneous event occurred <23 Ma and was highly heterogeneous in terms of volcanic products and petrographic varieties, but with predominance of quartzlatites. The dacite-andesites (first event) and the quartzlatites (second event) are geochemically similar and display a calc-alkaline affinity and highly incompatible element enriched patterns on spider diagrams, but the younger quartzlatites are richer in K2O, Rb and Ba and poorer in Sr. This is taken as evidence that mixing between an ultrapotassic lamprophyre/lamproite magma and an acid calc-alkaline (dacite-like) magma was essential petrogenetic processes during the second event. The proposed simplified volcanological model suggests that this mixing was responsible for triggering strongly explosive volcanic activity as well as for providing conditions for active hydrothermal and mineralization processes. The observed link between a specific magmatic phase and ore deposit formation can be a general phennomenon in the Balkans, and must be addressed by further and more advanced studies.
This paper provides new geochemical data focusing on valuable elements in the coal, parting, and floor samples in the No. 5 coal seam of the Taiyuan Formation from the Wujiawan mine, Datong coalfield, northern China. The minerals mainly consist of kaolinite, calcite, and pyrite, as well as trace amounts of quartz and illite. The No. 5 coal is enriched in Li, Ga, high field strength elements (HFSEs), and rare earth elements and yttrium (REY) when compared with world hard coals. Of particular interest is the high average concentration of Li (67.66 μg/g), which is around seven times higher than the value for world hard coals. Lithium, Ga, and HFSEs have strong inorganic affinities, whereas REY have organic affinities. The main carrier of Li, Ga, and HFSEs is aluminosilicate minerals, while REY appear to occur with organophosphorus. These HFSEs are enriched, both in the parting and in the adjacent coal samples. This suggests that these elements are likely to leach out during the diagenetic process. The distribution patterns of REY, along with the ratio of Al2O3/TiO2 and the figure of Zr/TiO2 vs. Nb/Y are suggestive of their derivation from felsic parent material. In the northern and eastern part of the Datong coalfield, there are several regions where the Li content is higher than the mineable grade, in particular in the northern Datong coalfield where there is a mine with an Li content of 294.6 μg/g. This is significantly higher than the mineable grade. Therefore, there is a potential for financially viable recovery of Li in these coals of the Datong coalfield.
The Early Permian coal is of great value in the Tengxian Coalfield, Shandon Province, Eastern China. This work deals with the new data focusing on mineralogical characteristics in the Early Permian Shanxi Formation No. 3 coal from the Jinyuan Mine. The Jinyuan coal is a low ash and highly volatile A bituminous coal. Minerals in the No. 3 coal mainly comprise of kaolinite, ankerite, illite, calcite, siderite, and quartz, with varying compositions of trace amounts of pyrite, jarosite, bassanite, anatase, and rutile. According to mineral assemblage in the coal plies, three Types (A to C) can be identified in the No. 3 coal. The dominant minerals in Type A are poorly-ordered kaolinite, illite, quartz, pyrite, and jarosite. Type B is mainly composed of well-ordered kaolinite, illite, siderite, ankerite, and calcite. Type C, with just one sample (JY-3-7c), which contains high proportions of calcite (54%) and ankerite (34%). Terrigenous minerals are elevated in coal plies that typically have relatively high contents of ash yield. The formation of syngenetic pyrite was generally due to seawater, while the sulphate minerals (jarosite and coquimbite) were derived from the oxidation of pyrite. Epigenetic vein-like or fracture-fillings carbonate minerals (ankerite, calcite, and siderite), kaolinite, and pyrite, as well as authigenic quartz were derived from the influx of hydrothermal fluids during different periods, from the authigenic to epigenetic. The paragonite in the coal may have been formed by the precipitated from Na-rich hydrothermal fluids. No effects of magmatic intrusion on mineralogy were investigated in this research.
Background: Point of care devices for performing targeted coagulation substitution in bleeding patients have become increasingly important in recent years. New on the market is the Quantra® from HemoSonics (LC, Charlottesville, VA, US). It uses sonorheometry, a sonic estimation of elasticity via resonance (SEER), a novel ultrasound-based technology that measures viscoelastic properties of whole blood. Several studies have already shown the comparability with devices already established on the market such as the ROTEM® (TEM International GmbH, Munich, Germany).
Objective: In contrast to existing studies, the planned study will be the first prospective interventional study using the new Quantra® system in a cardiac surgical patient cohort. The aim is to investigate the non-inferiority between an already existing coagulation algorithm, based on ROTEM®/Multiplate®, and a new algorithm based on the Quantra®, for the treatment of coagulopathic cardiac surgical patients.
Methods: The study is divided into two phases. In an initial observation phase, whole blood samples of 20 patients will be analyzed using both ROTEM®/Multiplate® and Quantra® obtained at three defined points of time (prior to surgery, after completion of cardiopulmonary bypass, on arrival in the intensive care unit). The obtained threshold values will be used to create an algorithm for hemotherapy. In a second intervention phase, the new algorithm will be tested against an algorithm used routineously for years at our department for non-inferiority.
Results: The main objective of the examination is the cumulative loss of blood within 24 hours after surgery. Statistical calculations based on literature and in-house data suggest that the new algorithm is not inferior if the difference in cumulative blood loss is < 150ml/24 h.
Conclusions: Because of the comparability of the Quantra® sonorheometry system with ROTEM® rotational thromboelastometric measurement methods, the existing hemotherapy treatment algorithm can be adapted to the Quantra device with a proof of non-inferiority. Clinical Trial: International Registered Report Identifier (IRRID): clinicaltrials.gov: NCT03902275
Inclusions of breyite (previously known as walstromite-structured CaSiO3) in diamond are usually interpreted as retrogressed CaSiO3 perovskite trapped in the transition zone or the lower mantle. However, the thermodynamic stability field of breyite does not preclude its crystallization together with diamond under upper-mantle conditions (6–10 GPa). The possibility of breyite forming in subducted sedimentary material through the reaction CaCO3 + SiO2 = CaSiO3 + C + O2 was experimentally evaluated in the CaO–SiO2–C–O2 ± H2O system at 6–10 GPa, 900–1500 ∘C and oxygen fugacity 0.5–1.0 log units below the Fe–FeO (IW) buffer. One experimental series was conducted in the anhydrous subsystem and aimed at determining the melting temperature of the aragonite–coesite (or stishovite) assemblage. It was found that melting occurs at a lower temperature (∼1500 ∘C) than the decarbonation reaction, which indicates that breyite cannot be formed from aragonite and silica under anhydrous conditions and an oxygen fugacity above IW – 1. In the second experimental series, we investigated partial melting of an aragonite–coesite mixture under hydrous conditions at the same pressures and redox conditions. The melting temperature in the presence of water decreased strongly (to 900–1200 ∘C), and the melt had a hydrous silicate composition. The reduction of melt resulted in graphite crystallization in equilibrium with titanite-structured CaSi2O5 and breyite at ∼1000 ∘C. The maximum pressure of possible breyite formation is limited by the reaction CaSiO3 + SiO2 = CaSi2O5 at ∼8 GPa. Based on the experimental results, it is concluded that breyite inclusions found in natural diamond may be formed from an aragonite–coesite assemblage or carbonate melt at 6–8 GPa via reduction at high water activity.
The crystal structure of MgCO3-II has long been discussed in the literature where DFT-based model calculations predict a pressure-induced transition of the carbon atom from the sp2 to the sp3 type of bonding. We have now determined the crystal structure of iron-bearing MgCO3-II based on single-crystal X-ray diffraction measurements using synchrotron radiation. We laser-heated a synthetic (Mg0.85Fe0.15)CO3 single crystal at 2500 K and 98 GPa and observed the formation of a monoclinic phase with composition (Mg2.53Fe0.47)C3O9 in the space group C2/m that contains tetrahedrally coordinated carbon, where CO44− tetrahedra are linked by corner-sharing oxygen atoms to form three-membered C3O96− ring anions. The crystal structure of (Mg0.85Fe0.15)CO3 (magnesium iron carbonate) at 98 GPa and 300 K is reported here as well. In comparison with previous structure-prediction calculations and powder X-ray diffraction data, our structural data provide reliable information from experiments regarding atomic positions, bond lengths, and bond angles.
Stability of halocarbons in whole air samples from the upper
troposphere and lowermost stratosphere
(2019)
Measurements of halogenated hydrocarbons of ambient air frequently rely on canister sampling followed by offline laboratory analysis. This allows for a large number of compounds to be analysed under stable conditions, maximising measurement precision. However, individual compounds might be affected during storage of canister samples. In order to assess halocarbon stability in whole air samples from the upper troposphere and lowermost stratosphere, we performed stability tests using the air sampling unit High REsolution Sampler (HIRES) which is part of the CARIBIC (Civil Aircraft for the Regular Investigation of the Atmosphere Based on an Instrument Container) instrument package. HIRES holds 88 light-weight stainless steel cylinders that are pressurized in flight to 4.5 bar using metal bellows pumps. The HIRES sampling unit was first deployed in 2010, but has up to now not been used for regular halocarbon analysis with exception of chloromethane. The sample collection unit was tested for sampling and storage effects of 28 halogenated compounds. The focus was on compound stability in the stainless steel canisters during storage of up to five weeks and on the influence of ozone, since flights take place in the upper troposphere and lowermost stratosphere with ozone mixing ratios of up to several hundred ppbV. Most of the investigated (hydro)chlorofluorocarbons and long-lived hydrofluorocarbons were found to be stable over a storage time of up to five weeks and were unaltered by ozone being present during pressurization. Some compounds such as for example dichloromethane, trichloromethane and tetrachloroethene started to decrease in the canisters after a storage time of more than two weeks or exhibited lowered mixing ratios in samples pressurized with ozone present. Few compounds such as for example tetrachloromethane and tribromomethane were found to be not stable in the HIRES stainless-steel canisters independent of ozone levels. Also growth was observed during storage, namely for HFC-152a and HFC-23.
Measurements of halogenated trace gases in ambient air frequently rely on canister sampling followed by offline laboratory analysis. This allows for a large number of compounds to be analysed under stable conditions, maximizing measurement precision. However, individual compounds might be affected during the sampling and storage of canister samples. In order to assess halocarbon stability in whole-air samples from the upper troposphere and lowermost stratosphere, we performed stability tests using the high-resolution sampler (HIRES) air sampling unit, which is part of the Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container (CARIBIC) instrument package. The HIRES unit holds 88 lightweight stainless-steel cylinders that are pressurized in flight to 4.5 bar using metal bellows pumps. The HIRES unit was first deployed in 2010 but has up to now not been used for regular halocarbon analysis with the exception of chloromethane analysis. The sample collection unit was tested for the sampling and storage effects of 28 halogenated compounds. The focus was on compound stability in the stainless-steel canisters during storage of up to 5 weeks and on the influence of ozone, since flights take place in the upper troposphere and lowermost stratosphere with ozone mixing ratios of up to several hundred parts per billion by volume (ppbv). Most of the investigated (hydro)chlorofluorocarbons and long-lived hydrofluorocarbons were found to be stable over a storage time of up to 5 weeks and were unaltered by ozone being present during pressurization. Some compounds such as dichloromethane, trichloromethane, and tetrachloroethene started to decrease in the canisters after a storage time of more than 2 weeks or exhibited lowered mixing ratios in samples pressurized with ozone present. A few compounds such as tetrachloromethane and tribromomethane were found to be unstable in the HIRES stainless-steel canisters independent of ozone levels. Furthermore, growth was observed during storage for some species, namely for HFC-152a, HFC-23, and Halon 1301.
A list of authors and their affiliations appears at the end of the paper New-particle formation is a major contributor to urban smog, but how it occurs in cities is often puzzling. If the growth rates of urban particles are similar to those found in cleaner environments (1–10 nanometres per hour), then existing understanding suggests that new urban particles should be rapidly scavenged by the high concentration of pre-existing particles. Here we show, through experiments performed under atmospheric conditions in the CLOUD chamber at CERN, that below about +5 degrees Celsius, nitric acid and ammonia vapours can condense onto freshly nucleated particles as small as a few nanometres in diameter. Moreover, when it is cold enough (below −15 degrees Celsius), nitric acid and ammonia can nucleate directly through an acid–base stabilization mechanism to form ammonium nitrate particles. Given that these vapours are often one thousand times more abundant than sulfuric acid, the resulting particle growth rates can be extremely high, reaching well above 100 nanometres per hour. However, these high growth rates require the gas-particle ammonium nitrate system to be out of equilibrium in order to sustain gas-phase supersaturations. In view of the strong temperature dependence that we measure for the gas-phase supersaturations, we expect such transient conditions to occur in inhomogeneous urban settings, especially in wintertime, driven by vertical mixing and by strong local sources such as traffic. Even though rapid growth from nitric acid and ammonia condensation may last for only a few minutes, it is nonetheless fast enough to shepherd freshly nucleated particles through the smallest size range where they are most vulnerable to scavenging loss, thus greatly increasing their survival probability. We also expect nitric acid and ammonia nucleation and rapid growth to be important in the relatively clean and cold upper free troposphere, where ammonia can be convected from the continental boundary layer and nitric acid is abundant from electrical storms.
Micromorphology is a suitable method to study the contents and stratigraphic relationships of pit fills. Within the ramparts of Corneşti-Iarcuri, fill layers of a pit were sampled. Th e pit fill was macroscopically divided into primary and secondary fill due to striking differences. These differences could be verified and concretized micromorphologically.
Diamond formation in the Earth has been extensively discussed in recent years on the basis of geochemical analysis of natural materials, high-pressure experimental studies, or theoretical aspects. Here, we demonstrate experimentally for the first time, the spontaneous crystallization of diamond from CH4-rich fluids at pressure, temperature and redox conditions approximating those of the deeper parts of the cratonic lithospheric mantle (5-7 GPa) without using diamond seed crystals or carbides. In these experiments the fluid phase is nearly pure methane, even though the oxygen fugacity was significantly above metal saturation. We propose several previously unidentified mechanisms that may promote diamond formation under such conditions and which may also have implications for the origin of sublithospheric diamonds. These include the hydroxylation of silicate minerals like olivine and pyroxene, H2 incorporation into these phases and the "etching" of graphite by H2 and CH4 and reprecipitation as diamond. This study also serves as a demonstration of our new high-pressure experimental technique for obtaining reduced fluids, which is not only relevant for diamond synthesis, but also for investigating the metasomatic origins of diamond in the upper mantle, which has further implications for the deep carbon cycle.
The frequency of extreme events has changed, having a direct impact on human lives. Regional climate models help us to predict these regional climate changes. This work presents an atmosphere–ocean coupled regional climate system model (RCSM; with the atmospheric component COSMO-CLM and the ocean component NEMO) over the European domain, including three marginal seas: the Mediterranean, North, and Baltic Sea. To test the model, we evaluate a simulation of more than 100 years (1900–2009) with a spatial grid resolution of about 25 km. The simulation was nested into a coupled global simulation with the model MPI-ESM in a low-resolution configuration, whose ocean temperature and salinity were nudged to the ocean–ice component of the MPI-ESM forced with the NOAA 20th Century Reanalysis (20CR). The evaluation shows the robustness of the RCSM and discusses the added value by the coupled marginal seas over an atmosphere-only simulation. The coupled system is stable for the complete 20th century and provides a better representation of extreme temperatures compared to the atmosphere-only model. The produced long-term dataset will help us to better understand the processes leading to meteorological and climate extremes.
The most frequently used boundary-layer turbulence parameterization in numerical weather prediction (NWP) models are turbulence kinetic energy (TKE) based-based schemes. However, these parameterizations suffer from a potential weakness, namely the strong dependence on an ad-hoc quantity, the so-called turbulence length scale. The physical interpretation of the turbulence length scale is difficult and hence it cannot be directly related to measurements or large eddy simulation (LES) data. Consequently, formulations for the turbulence length scale in basically all TKE schemes are based on simplified assumptions and are model-dependent. A good reference for the independent evaluation of the turbulence length scale expression for NWP modeling is missing. Here we propose a new turbulence length scale diagnostic which can be used in the gray zone of turbulence without modifying the underlying TKE turbulence scheme. The new diagnostic is based on the TKE budget: The core idea is to encapsulate the sum of the molecular dissipation and the cross-scale TKE transfer into an effective dissipation, and associate it with the new turbulence length scale. This effective dissipation can then be calculated as a residuum in the TKE budget equation (for horizontal sub-domains of different sizes) using LES data. Estimation of the scale dependence of the diagnosed turbulence length scale using this novel method is presented for several idealized cases.
Metasomatic evolution of coesite-bearing diamondiferous eclogite from the Udachnaya Kimberlite
(2020)
A coesite-bearing diamondiferous eclogite from the Udachnaya kimberlite (Daldyn field, Siberian craton) has been studied to trace its complex evolution recorded in rock-forming and minor mineral constituents. The eclogite sample is composed of rock-forming omphacite (60 vol%), garnet (35 vol%) and quartz/coesite (5 vol%) and contains intergranular euhedral zoned olivine crystals, up to 200 µm long, coexisting with phlogopite, orthopyroxene, clinopyroxene (secondary), K-feldspar, plagioclase, spinel, sodalite and djerfisherite. Garnet grains are zoned, with a relatively homogeneous core and a more magnesian overgrowth rim. The rim zones further differ from the core in having higher Zr/Y (6 times that in the cores), ascribed to interaction with, or precipitation from, a kimberlite-related melt. Judging by pressure-temperature estimates (~1200 °C; 6.2 GPa), the xenolith originated at depths of ~180–200 km at the base of the continental lithosphere. The spatial coexistence of olivine, orthopyroxene and coesite/quartz with K-Na-Cl minerals in the xenolith indicates that eclogite reacted with a deep-seated kimberlite melt. However, Fe-rich olivine, orthopyroxene and low-pressure minerals (sodalite and djerfisherite) likely result from metasomatic reaction at shallower depths during transport of the eclogite by the erupting kimberlite melt. Our results demonstrate that a mixed eclogitic-peridotitic paragenesis, reported previously from inclusions in diamond, can form by interaction of eclogite and a kimberlite-related melt.
Vegetation responds to drought through a complex interplay of plant hydraulic mechanisms, posing challenges for model development and parameterization. We present a mathematical model that describes the dynamics of leaf water-potential over time while considering different strategies by which plant species regulate their water-potentials. The model has two parameters: the parameter λ describing the adjustment of the leaf water potential to changes in soil water potential, and the parameter Δψww describing the typical ‘well-watered’ leaf water potentials at non-stressed (near-zero) levels of soil water potential. Our model was tested and calibrated on 110 time-series datasets containing the leaf- and soil water potentials of 66 species under drought and non-drought conditions. Our model successfully reproduces the measured leaf water potentials over time based on three different regulation strategies under drought. We found that three parameter sets derived from the measurement data reproduced the dynamics of 53% of an drought dataset, and 52% of a control dataset [root mean square error (RMSE) < 0.5 MPa)]. We conclude that, instead of quantifying water-potential-regulation of different plant species by complex modeling approaches, a small set of parameters may be sufficient to describe the water potential regulation behavior for large-scale modeling. Thus, our approach paves the way for a parsimonious representation of the full spectrum of plant hydraulic responses to drought in dynamic vegetation models.
Inappropriate land management leads to soil loss with destruction of the land’s resource and sediment input into the receiving river. Part of the sediment budget of a catchment is the estimation of soil loss. In the Ruzizi catchment in the Eastern Democratic Republic of the Congo (DRC), only limited research has been conducted on soil loss mainly dealing with local observations on geomorphological forms or river load measurements; a regional quantification of soil loss is missing so far. Such quantifications can be calculated using the Universal Soil Loss Equation (USLE). It is composed of four factors: precipitation (R), soil (K), topography (LS), and vegetation cover (C). The factors can be calculated in different ways according to the characteristics of the study area. In this paper, different approaches for calculating the single factors are reviewed and validated with field work in two sub-catchments of Ruzizi River supplying the water for the reservoirs of Ruzizi I and II hydroelectric dams. It became obvious that the (R)USLE model provides the best results with revised R and LS factors. C factor calculations required to conduct a supervised classification using the Maximum Likelihood Procedure. Different C factor values were assigned to the land cover classes. The calculations resulted in a soil loss rate for the predominantly occurring Ferralsols and Leptosols of around 576 kt/yr in both catchments, when 2016 landcover and precipitation are used. This represents an area-normalized value of 40.4 t/ha/yr for Ruzizi I and 50.5 t/ha/yr for Ruzizi II due to different landcover in the two sub-catchments. The mean value for the whole study area is 47.8 t/ha/yr or even 27.1 t/ha/yr when considering land management techniques like terracing on the slopes (P factor). This work has shown that the (R)USLE model can serve as an easy to handle tool for soil loss quantification when comprehensive field work results are sparse. The model can be implemented in Geographic Information Systems (GIS) with free data; hence, a validation is crucial. It becomes apparent that the use of high resolution Sentinel 2a MSI data as the basis for C factor calculations is an appropriate method for considering heterogeneous Land Use Land Cover (LULC) patterns. To transfer the approach to other regions, the calculation of factor R needs to be modified
Accretion rates of Holocene tropical coral reefs in three areas in the Atlantic, Pacific and Indian Oceans have been quantified in 79 dated core sections in 34 reef cores from Belize, the Maldives and French Polynesia. Holocene vertical reef accretion rate averages 5.05 m/kyr and has decreased during the past 10 kyr. Accretion rates in branched and massive coral facies are statistically similar. Reef accretion rate is positively correlated with the rate of sea‐level rise, that is the degree of creation of accommodation space, and with climate as expressed in a Holocene sea surface temperature anomaly. Accommodation space is also created by subsidence, but at a rate one to two orders of magnitude lower than that created by glacio‐eustasy (0.04 to 0.16 m/kyr). Lagoonal background sedimentation in adjacent reef lagoons averages 0.89 m/kyr as measured in 72 dated core sections in 28 cores. Lagoonal carbonate sedimentation on top of underlying mangrove peat usually starts after a considerable hiatus of ca 3 kyr on average. The lagoonal background sedimentation rate increased during the Holocene, probably due to deepening. The differences between vertical reef accretion and lagoonal background sedimentation rates are a major factor in the production of the widely known saucer shapes typical of tropical reefs and carbonate platforms, that is the creation of unfilled accommodation space. Reef core recovery, used as a proxy for reef consolidation, and core depth exhibit a statistically negative correlation based on data from 326 core barrels. Recovery and marine cement abundance (average volume 8.6%) also decrease from windward to leeward core positions. These observations are presumably a result of both a decrease in the rate of sea‐level rise that is the increase in time available for submarine cementation during the Holocene and the amount of flushing of reef interstices by marine waters.
Diurnal valley winds frequently form over complex topography, particularly under fair weather conditions, and have a significant impact on the local weather and climate. Since diurnal valley winds result from complex and multi-scale interactions, their representation in numerical weather prediction models is challenging. Better understanding of these local winds based on observations is crucial to improve the accuracy of the forecasts. This study investigates the diurnal evolution of the three-dimensional mean wind structure in a deep Alpine valley, the Rhone valley at Sion, using data from a radar wind profiler and a surface weather station operated continuously from 1 September 2016 to 17 July 2017. In particular, the wind profiler data was analyzed for a subset of days on which fair weather conditions allowed for the full development of thermally driven winds. A pronounced diurnal cycle of the wind speed, as well as a reversal of the wind direction twice per day is documented for altitudes up to about 2 km above ground level (AGL) in the warm season and less than 1 km AGL in winter. The diurnal pattern undergoes significant changes during the course of the year. Particularly during the warm-weather months of May through to September, a low-level wind maximum occurs, where mean maximum up-valley velocities of 8–10 m s−1 are found between 15–16 UTC at altitudes around 200 m AGL. In addition, during nighttime, a down-valley jet with maximum wind speeds of 4–8 m s−1 around 1 km AGL is found. A case study of a three-day period in September 2016 illustrates the occurrence of an elevated layer of cross-valley flow around 1–1.5 km AGL.
Cenozoic lignite deposits are widespread across Europe, Asia, America, Australia, and Indonesia. These deposits were the subject of numerous studies on changes in regional/global paleoclimates, paleobotany, paleoenvironment, and basin evolutions, which led to the formation of these lignites. In some of these Cenozoic lignite deposit basins, a succession of pale and dark lignite layers has been described in the Miocene Lower Rhine Basin in Germany, the Oligo-Miocene Gippsland Basin in southeastern Australia, and several Mio-Pliocene basins in southwestern China. Furthermore, pale and dark lithotypes in lignite seams also have been found in some Pliocene lignite deposit basins from Slovenia, Serbia, and Poland. The widespread cyclic occurrence of pale and dark layers in lignite basins might represent alternating depositional conditions related to the changes in plant communities, the regional/global climate, the tectonic setting, the Asian monsoon, and orbital periodicity during peat formation. ...
Under the Kigali Amendment to the Montreal Protocol, new controls are being implemented to reduce emissions of HFC-23 (CHF3), a by-product during the manufacture of HCFC-22 (CHClF2). Starting in 2015, China and India, who dominate global HCFC-22 production (75% in 2017), set out ambitious programs to reduce HFC-23 emissions. Here, we estimate that these measures should have seen global emissions drop by 87% between 2014 and 2017. Instead, atmospheric observations show that emissions have increased and in 2018 were higher than at any point in history (15.9 ± 0.9 Gg yr−1). Given the magnitude of the discrepancy between expected and observation-inferred emissions, it is likely that the reported reductions have not fully materialized or there may be substantial unreported production of HCFC-22, resulting in unaccounted-for HFC-23 by-product emissions. The difference between reported and observation-inferred estimates suggests that an additional ~309 Tg CO2-equivalent emissions were added to the atmosphere between 2015 and 2017.
Groundwater is the largest source of accessible freshwater with its dynamics having significantly changed due to human withdrawals, and being projected to continue to as a result of climate change. The pumping of groundwater has led to lowered water tables, decreased base flow, and depletion.
Global hydrological models (GHMs) are used to simulate the global freshwater cycle, assessing impacts of changes in climate and human freshwater use. Currently, groundwater is commonly represented by a bucket-like linear storage component in these models. Bucket models, however, cannot provide information on the location of the groundwater table. Due to this limitation, they can only simulate groundwater discharge to surface water bodies but not recharge from surface water to groundwater and calculate no lateral and vertical groundwater flow whatsoever among grid cells. For instance this may lead to an underestimation of groundwater resources in semiarid areas, where groundwater is often replenished by surface water. In order to overcome these limitations it is necessary to replace the linear groundwater model in GHMs with a hydraulic head gradient-based groundwater flow model
This thesis presents the newly developed global groundwater model G3M and its coupling to the GHM WaterGAP spanning over 70,000 lines of newly developed code. Development and validation of the modeling software are discussed along with numerical challenges. Based on the newly developed software, a global natural equilibrium groundwater model is presented showing better agreements with observations than previous models. Groundwater discharge to rivers is found to be the most dominant flow component globally, compared to flows to other surface water bodies and lateral flows. Furthermore, first global maps of the distribution of gaining and losing surface water bodies are displayed.
For the purpose of determining the uncertainty in model outcomes a sensitivity study is conducted with an innovative approach through applying a global sensitivity analysis for a computationally complex model. First global maps of spatially distributed parameter sensitivities are presented. The results at hand indicate that globally simulated hydraulic heads are equally sensitive to hydraulic conductivity, groundwater recharge and surface water body elevation, even though parameter sensitivities do vary regionally.
A high resolution model of New Zealand is developed to further understand the involved uncertainties connected to the spatial resolution of the global model. This thesis finds that a new understanding is necessary how these models can be evaluated and that a simple increase in spatial resolution is not improving the model performance when compared to observations.
Alongside the assessment of the natural equilibrium, the concept of a fully coupled transient model as integrated storage component replacing the former model in the hydrological model WaterGAP is discussed. First results reveal that the model shows reasonable response to seasonal variability although it contains persistent head trends leading to global overestimates of water table depth due to an incomplete coupling. Nonetheless, WaterGAP-G3M is already able to show plausible long term storage trends for areas that are known to be affected by groundwater depletion. In comparison with two established regional models in the Central Valley the coupled model shows a highly promising simulation of storage declines.
The endemic argan tree (Argania spinosa) populations in South Morocco are highly degraded due to their use as a biomass resource in dry years and illegal firewood extraction. The intensification and expansion of agricultural land lead to a retreat of the wooded area, while the remaining argan open woodlands are often overgrazed. Thus, canopy-covered areas decrease while areas without vegetation cover between the argan trees increase. In total, 36 rainfall simulation experiments as well as 60 infiltration measurements were conducted to investigate the potential difference between tree-covered areas and bare intertree areas. In addition, 60 soil samples were taken under the trees and in the intertree areas parallel to the contour lines. Significant differences using a t-test were found between tree and intertree areas for the studied parameters Ksat, Kh, pH, electric conductivity, percolation stability, total C-content, total N-content, K-content, Na-content, and Mg-content. Surface runoff and soil losses were not as conclusive but showed similar trends. The results showed that argan trees influence the soil underneath significantly, while the soil in intertree areas is less protected and more degraded. It is therefore reasonable to assume further degradation of the soil when intertree areas extend further due to lack of rejuvenation of argan trees.
Invasive plant species are increasingly altering species composition and the functioning of ecosystems from a local to a global scale. The grass species Pennisetum setaceum has recently raised concerns as an invader on different archipelagos worldwide. Among these affected archipelagos are the Canary Islands, which are a hotspot of endemism. Consequently, conservation managers and stakeholders are interested in the potential spreading of this species in the archipelago. We identify the current extent of the suitable habitat for P. setaceum on the island of La Palma to assess how it affects island ecosystems, protected areas (PAs), and endemic plant species richness. We recorded in situ occurrences of P. setaceum from 2010 to 2018 and compiled additional ones from databases at a 500 m × 500 m resolution. To assess the current suitable habitat and possible distribution patterns of P. setaceum on the island, we built an ensemble model. We projected habitat suitability for island ecosystems and PAs and identified risks for total as well as endemic plant species richness. The suitable habitat for P. setaceum is calculated to cover 34.7% of the surface of La Palma. In open ecosystems at low to mid elevations, where native ecosystems are already under pressure by land use and human activities, the spread of the invader will likely lead to additional threats to endemic plant species. Forest ecosystems (e.g., broadleaved evergreen and coniferous forests) are not likely to be affected by the spread of P. setaceum because of its heliophilous nature. Our projection of suitable habitat of P. setaceum within ecosystems and PAs on La Palma supports conservationists and policymakers in prioritizing management and control measures and acts as an example for the potential threat of this graminoid invader on other islands.
Often in climate system studies, linear and symmetric statistical measures are applied to quantify interactions among subsystems or variables. However, they do not allow identification of the driving and responding subsystems. Therefore, in this study, we aimed to apply asymmetric measures from information theory: the axiomatically proposed transfer entropy and the first principle-based information flow to detect and quantify climate interactions. As their estimations are challenging, we initially tested nonparametric estimators like transfer entropy (TE)-binning, TE-kernel, and TE k-nearest neighbor and parametric estimators like TE-linear and information flow (IF)-linear with idealized two-dimensional test cases along with their sensitivity on sample size. Thereafter, we experimentally applied these methods to the Lorenz-96 model and to two real climate phenomena, i.e., (1) the Indo-Pacific Ocean coupling and (2) North Atlantic Oscillation (NAO)–European air temperature coupling. As expected, the linear estimators work for linear systems but fail for strongly nonlinear systems. The TE-kernel and TE k-nearest neighbor estimators are reliable for linear and nonlinear systems. Nevertheless, the nonparametric methods are sensitive to parameter selection and sample size. Thus, this work proposes a composite use of the TE-kernel and TE k-nearest neighbor estimators along with parameter testing for consistent results. The revealed information exchange in Lorenz-96 is dominated by the slow subsystem component. For real climate phenomena, expected bidirectional information exchange between the Indian and Pacific SSTs was detected. Furthermore, expected information exchange from NAO to European air temperature was detected, but also unexpected reversal information exchange. The latter might hint to a hidden process driving both the NAO and European temperatures. Hence, the limitations, availability of time series length and the system at hand must be taken into account before drawing any conclusions from TE and IF-linear estimations.
Enhanced aridification of Central Asia driven by the combined effects of orogenic surface uplift, Paratethys retreat, changes in atmospheric moisture transport and global cooling is one of the most prominent Cenozoic climate change events of the Northern Hemisphere. Deciphering regional long-term patterns of Central Asian hydrology is, therefore, a key element in understanding the role of Northern Hemisphere mid-latitude drying in the global hydrological system. Pedogenic carbonates record information of the paleoecosystem, the paleogeography, hydrology, tectonic and climatic conditions as well as the sedimentary regime during the time in which they formed. The calcrete-bearing paleosols in continental sedimentary basins yield the possibility for understanding these processes, mechanisms and controlling factors. This study characterizes long-term paleoenvironmental conditions between the late Oligocene and early Miocene in SE Kazakhstan based on stable isotopes, elemental geochemistry and laser ablation U-Pb geochronology from alluvial, fluvial and pedogenic deposits. The main topics addressed in this thesis are paleosol and calcrete formation processes in the light of geochemistry, tectonic and climatic influences on both, as well as the paleoenvironmental and hydrological conditions which led to these processes.
The sedimentological succession of the 14 km-long Kendyrlisai Valley in the Ili Basin, SE Kazakhstan in Central Asia, yields exceptional well-developed paleosols which provide an insight into the relationship between tectonics and sedimentation as well as soil formation processes. The valley accommodates more than 600 m of siliciclastic sediments deposited in a fluvial to alluvial environment in the lower part which grade into lacustrine to fluvial deposition with minor gypsum accumulation in the upper part. The yet undated sediments of Kendyrlisai Valley are compared with a biostratigraphically dated and well described succession in an adjacent location. The correlation of the two successions revealed a proximal-distal relation with the Kendyrlisai Valley succession represents the basin margin position with coarse alluvial-fluvial sediments. The calcrete nodules in Kendyrlisai Valley paleosols give the opportunity of U-Pb dating with LA-ICP-MS which uses the variation in both U and Pb to directly date the calcite. The U-Pb dating revealed a late Oligocene-early Miocene age for the investigated section. The analysis of facies and geochemistry of the paleosol profiles in Kendyrlisai Valley gives insight into calcretization stages, pedogenic processes and landscape stability. Kendyrlisai Valley paleosols show a low to moderate weathering intensity with the highest weathering intensity between 0.5 and 0.8 m depth in the paleosol profile. The comparison between acid leachable and non-acid leachable fraction indicate an incorporation of Ca and Ba in incipient calcrete calcite, whereas clay minerals adsorb Mg and Sr. During the evolution from early to more mature calcrete stages, i.e. calcrete nodules, Ba is lost by dissolution and subsequently adsorbed on clay minerals. The nodules consist almost exclusively of pure calcium carbonate with rare substitution of Ca by Mg indicating a constant supply of Ca by weathering and solution during calcrete formation. The occurrence of Mg-bearing clay minerals indicates high evaporative conditions with alkaline waters (pH >9).
Sampled calcrete nodule cross sections reveal more than one weathering and calcrete formation phase with a higher supply of Ca, Mg and Fe during early phases. The organic and inorganic carbon isotope composition of the calcrete nodules reflects C3 metabolism under occasionally moisture stress, resulting in higher δ13C values and lower respiration rates. This study also presents calculated atmospheric pCO2 values from the calcrete nodules with the equation from Cerling et al. (1999). The average calculated CO2 concentration for Kendyrlisai Valley paleosols is 313 ± 110 ppmv. The comparison with data from other studies during the late Oligocene–early Miocene reveal lower values for Kendyrlisai Valley paleosols, which may stem from an underestimation of the plant-respired CO2.
The knowledge of the variability within the paleosols and calcrete nodules enables a reliable paleoclimatic interpretation for the Kendyrlisai Valley and beyond the Ili Basin. Sedimentary facies and geochemical weathering indices suggest an increased surface and groundwater discharge fed by orographically-enhanced precipitation in the Tien Shan hinterland. In contrast, pedogenic stable isotope data and elevated rates of Mg fixation in clay minerals mirror enhanced rates of evaporation in the vadose zone due to protracted aridification. This study posits that pronounced surface uplift of the Tien Shan Mountains during the Oligocene–Miocene transition promoted regionally increased orographic precipitation and the development of fluvial discharge systems.
The comparison with other studies in adjacent basins creates a precipitation pattern for Central Asia during the late Oligocene to early Miocene. The westerlies supplied Central Asia with atmospheric moisture from the West, possibly from the Eastern Paratethys. The uplifting Tien Shan Mountain ranges captured this moisture on their luv-side, resulting in a pronounced orographic rainfall in the adjacent Ili and Issyk Kul Basins. The Tarim Basin and the Valley of Lakes experienced drier conditions due to the rain shadow effect on the lee-side of the Tien Shan and Altai Mountains. In course of this findings, the thesis highlights the crucial role the Tien Shan Mountains play and had been playing in former times as an orographic barrier for the distribution of atmospheric moisture across Central Asia.
Convective shower characteristics simulated with the convection-permitting climate model COSMO-CLM
(2019)
This paper evaluates convective precipitation as simulated by the convection-permitting climate model (CPM) Consortium for Small-Scale Modeling in climate mode (COSMO-CLM) (with 2.8 km grid-spacing) over Germany in the period 2001–2015. Characteristics of simulated convective precipitation objects like lifetime, area, mean intensity, and total precipitation are compared to characteristics observed by weather radar. For this purpose, a tracking algorithm was applied to simulated and observed precipitation with 5-min temporal resolution. The total amount of convective precipitation is well simulated, with a small overestimation of 2%. However, the simulation underestimates convective activity, represented by the number of convective objects, by 33%. This underestimation is especially pronounced in the lowlands of Northern Germany, whereas the simulation matches observations well in the mountainous areas of Southern Germany. The underestimation of activity is compensated by an overestimation of the simulated lifetime of convective objects. The observed mean intensity, maximum intensity, and area of precipitation objects increase with their lifetime showing the spectrum of convective storms ranging from short-living single-cell storms to long-living organized convection like supercells or squall lines. The CPM is capable of reproducing the lifetime dependence of these characteristics but shows a weaker increase in mean intensity with lifetime resulting in an especially pronounced underestimation (up to 25%) of mean precipitation intensity of long-living, extreme events. This limitation of the CPM is not identifiable by classical evaluation techniques using rain gauges. The simulation can reproduce the general increase of the highest percentiles of cell area, total precipitation, and mean intensity with temperature but fails to reproduce the increase of lifetime. The scaling rates of mean intensity and total precipitation resemble observed rates only in parts of the temperature range. The results suggest that the evaluation of coarse-grained (e.g., hourly) precipitation fields is insufficient for revealing challenges in convection-permitting simulations.
The sources and critical enrichment processes for granite related tin ores are still not well understood. The Erzgebirge represents one of the classical regions for tin mineralization. We investigated the four largest plutons from the Western Erzgebirge (Germany) for the geochemistry of bulk rocks and autocrystic zircons and relate this information to their intrusion ages. The source rocks of the Variscan granites were identified as high-grade metamorphic rocks based on the comparison of Hf-O isotope data on zircons, the abundance of xenocrystic zircon ages as well as Nd and Hf model ages. Among these rocks, restite is the most likely candidate for later Variscan melts. Based on the evolution with time, we could reconstruct enrichment factors for tin and tungsten starting from the protoliths (575 Ma) that were later converted to high-grade metamorphic rocks (340 Ma) and served as sources for the older biotite granites (323–318 Ma) and the tin granites (315–314 Ma). This evolution involved a continuous enrichment of both tin and tungsten with an enrichment factor of ~15 for tin and ~7 for tungsten compared to the upper continental crust (UCC). Ore level concentrations (>10–100 times enrichment) were achieved only in the greisen bodies and dykes by subsequent hydrothermal processes.
Here we present a comprehensive attempt to correlate aragonitic Na∕Ca ratios from Desmophyllum pertusum (formerly known as Lophelia pertusa), Madrepora oculata and a caryophylliid cold-water coral (CWC) species with different seawater parameters such as temperature, salinity and pH. Living CWC specimens were collected from 16 different locations and analyzed for their Na∕Ca ratios using solution-based inductively coupled plasma-optical emission spectrometry (ICP-OES) measurements.
The results reveal no apparent correlation with salinity (30.1–40.57 g kg−1) but a significant inverse correlation with temperature (−0.31±0.04 mmolmol−1∘C−1). Other marine aragonitic organisms such as Mytilus edulis (inner aragonitic shell portion) and Porites sp. exhibit similar results highlighting the consistency of the calculated CWC regressions. Corresponding Na∕Mg ratios show a similar temperature sensitivity to Na∕Ca ratios, but the combination of two ratios appears to reduce the impact of vital effects and domain-dependent geochemical variation. The high degree of scatter and elemental heterogeneities between the different skeletal features in both Na∕Ca and Na∕Mg, however, limit the use of these ratios as a proxy and/or make a high number of samples necessary. Additionally, we explore two models to explain the observed temperature sensitivity of Na∕Ca ratios for an open and semi-enclosed calcifying space based on temperature-sensitive Na- and Ca-pumping enzymes and transport proteins that change the composition of the calcifying fluid and consequently the skeletal Na∕Ca ratio.
Recently, carbonates have attracted a lot of attention, due to the recognition of their importance in the global carbon cycle. This was enabled by improvement of the experimental techniques that allow for investigating the stability, structure, and physical properties of materials and high-pressures and high-temperatures, that is, they allow for investigating minerals and geochemical processes at the conditions occurring deep inside Earth. Although a lot of research has been focused on carbonates, there are still some open questions regarding their structure and physical properties at such extreme conditions. The aim of this thesis is to establish a deeper understanding of the nature of the phase transitions in carbonates by studying how do the atoms building up the crystal structure vibrate, that is lattice dynamics. The methodology adapted in this study is a combination of experimental and computational methods which allows for a very thorough examination of the problem. The computational approach allows to determine parameters that are elusive or tedious to measure, and the experimental results provide a solid benchmark for the calculations. This tandem of methods has been widely used for investigating lattice dynamics of various materials. In this study it was used to elucidate the structure and properties of carbonates in the deep Earth conditions
The Arctic Svalbard Archipelago hosts the world’s northernmost cold-water ‘carbonate factories’ thriving here despite of presumably unfavourable environmental conditions and extreme seasonality. Two contrasting sites of intense biogenic carbonate production, the rhodolith beds in Mosselbukta in the north of the archipelago and the barnacle-mollusc dominated carbonate sediments accumulating in the strong hydrodynamic regime of the Bjørnøy-Banken south of Spitsbergen, were the targets of the RV Maria S. Merian cruise 55 in June 2016. By integrating data from physical oceanography, marine biology, and marine geology, the present contribution characterises the environmental setting and biosedimentary dynamics of these two polar carbonate factories. Repetitive CTD profiling in concert with autonomous temperature/salinity loggers on a long-term settlement platform identified spatiotemporal patterns in the involved Atlantic and Polar water masses, whereas short-term deployments of a lander revealed fluctuations of environmental variables in the rhodolith beds in Mosselbukta and at same depth (46 m) at Bjørnøy-Banken. At both sites, dissolved inorganic nutrients in the water column were found depleted (except for elevated ammonium concentrations) and show an overall increase in concentration and N:P ratios toward deeper waters. This indicates that a recycling system was fuelling primary production after the phytoplankton spring bloom at the time of sampling in June 2016. Accordingly, oxygen levels were found elevated and carbon dioxide concentrations (pCO2) markedly reduced, on average only half the expected equilibrium values. Backed up by seawater stable carbon and oxygen isotope signatures, this is interpreted as an effect of limited air-sea gas exchange during seasonal ice cover in combination with a boost in community photosynthesis during the spring phytoplankton bloom. The observed trends are enhanced by the onset of rhodophyte photosynthesis in the rhodolith beds during the polar day upon retreat of sea-ice. Potential adverse effects of ocean acidification on the local calcifier community are thus predicted to be seasonally buffered by the marked drop in pCO2 during the phase of sea-ice cover and spring phyto-plankton bloom, but this effect will diminish should the seasonal sea-ice formation continue to decline. Among the 25 macrobenthos taxa identified from images captured by the lander’s camera system, all but three species were calcifiers contributing to the carbonate production. Biodiversity was found to be much higher in Mosselbukta (21 taxa) compared to Bjørnøy-Banken (8 taxa), which is considered as a result of enhanced habitat diversity provided in the rhodolith beds by the bioengineering crustose alga Lithothamnion glaciale. Filter-feeding activity of selected key species did reveal group-specific but no common activity patterns. Biotic disturbance of the filtering activity was common, in contrast to abiotic factors, with hermit crabs representing the primary trigger. Motion tracking of rhodoliths revealed a high frequency of dislocation, triggered not by abiotic factors but by the activity of benthic invertebrates, in particular echinoids ploughing below or moving over the rhodoliths. The echinoid Strongylocentrotus sp. is the most abundant component of the associated fauna, thereby considerably contributing both to carbonate production and to grazing bioerosion. Together, these results portray a high degree of seasonal as well as short-term dynamics in environmental conditions that despite many similarities support distinctly different communities and biodiversity patterns in the calcifying macrobenthos at the two studied polar carbonate factories.
The exchange of heat, momentum, and mass in the atmosphere over mountainous terrain is controlled by synoptic-scale dynamics, thermally driven mesoscale circulations, and turbulence. This article reviews the key challenges relevant to the understanding of exchange processes in the mountain boundary layer and outlines possible research priorities for the future. The review describes the limitations of the experimental study of turbulent exchange over complex terrain, the impact of slope and valley breezes on the structure of the convective boundary layer, and the role of intermittent mixing and wave–turbulence interaction in the stable boundary layer. The interplay between exchange processes at different spatial scales is discussed in depth, emphasizing the role of elevated and ground-based stable layers in controlling multi-scale interactions in the atmosphere over and near mountains. Implications of the current understanding of exchange processes over mountains towards the improvement of numerical weather prediction and climate models are discussed, considering in particular the representation of surface boundary conditions, the parameterization of sub-grid-scale exchange, and the development of stochastic perturbation schemes.
Atmospheric aerosols and their effect on clouds are thought to be important for anthropogenic radiative forcing of the climate, yet remain poorly understood1. Globally, around half of cloud condensation nuclei originate from nucleation of atmospheric vapours2. It is thought that sulfuric acid is essential to initiate most particle formation in the atmosphere3,4, and that ions have a relatively minor role5. Some laboratory studies, however, have reported organic particle formation without the intentional addition of sulfuric acid, although contamination could not be excluded6,7. Here we present evidence for the formation of aerosol particles from highly oxidized biogenic vapours in the absence of sulfuric acid in a large chamber under atmospheric conditions. The highly oxygenated molecules (HOMs) are produced by ozonolysis of α-pinene. We find that ions from Galactic cosmic rays increase the nucleation rate by one to two orders of magnitude compared with neutral nucleation. Our experimental findings are supported by quantum chemical calculations of the cluster binding energies of representative HOMs. Ion-induced nucleation of pure organic particles constitutes a potentially widespread source of aerosol particles in terrestrial environments with low sulfuric acid pollution.
Atmospheric nanoaerosols have extensive effects on the Earth’s climate and human health. This cumulative work focuses on the development and characterization of instrumentation for measuring various parameters of atmospheric nanoaerosols, and its use to understand new particle formation from organic precursors. The principal research question is, how the chemical composition of nanoaerosol particles can be measured and how atmospheric chemistry influences aerosol processes, especially new particle formation and growth. Therefore, nanoaerosols are investigated under various aspects. More specifically, an instrument is developed to analyze nanoparticles, and field as well as chamber studies are conducted.
The main project is the instrument development of the Thermal Desorption Differential Mobility Analyzer (TD-DMA, project 1, Wagner et al. (2018)). This instrument analyzes the chemical composition of small aerosol particles. By characterization and testing in chamber experiments, it is proven to be suitable for the analysis of freshly nucleated particles.
The second project (Wagner et al. (2017)) applies a broad spectrum of aerosol measurement instruments for the characterization of aerosol particles produced by a skyscraper blasting. A comprehensive picture of the particle population emitted by the demolition is obtained.
Project 3 (K¨urten et al. (2016)) is also an ambient aerosol measurement, focusing of new particle formation in a rural area in central Germany, and the ability of a negative nitrate CI-APi-TOF to detect various substances in atmosphere. Project 4 (Heinritzi et al. (2016)) is a characterization of the negative nitrate CI-APi-TOF used in projects 1, 3, 5, 6, 7 and 8. The following projects focus on understanding new particle formation from atmospherically abundant organic precursors. Key instruments comprise the negative nitrate CI-APiTOF for gas-phase measurements of the nucleating species, and various sizing and counting instruments for quantifying the particle formation and growth. Project 5 (Kirkby et al. (2016)) shows that biogenic organic compounds formed from alpha-pinene can nucleate on their own without the influence of e.g. sulfuric acid. Project 6 (Tr¨ostl et al. (2016)) describe the subsequent growth of these particles. Project 7 (Stolzenburg et al. (2018)) covers the temperature dependence of this growth and in project 8 (Heinritzi et al. (2018)), the suppressing influence of isoprene on the new particle formation is assessed.
We present a study characterizing aerosol particles resulting from a skyscraper blasting. High mass concentrations with a maximum of 844.9 μg m-3 were present for a short time period of approximately 15 minutes. They result in a day mean of 32.6 μg m-3 compared to a 27.6 μg m-3 background not exceeding the 50 μg m-3 EU maximum permissive value. The increase in particle number concentration was less pronounced with a maximum concentration of 6.9 ⋅ 104 cm-3 compared to the local background value of 1.8 ⋅ 104 cm-3. The size-resolved number concentration shows a single mode of ultrafine particles at approximately 93 nm. The spatial distribution of deposited dust was investigated with Bergerhoff glass collection vessels, showing a decrease with distance. In the deposited dust samples the concentrations of twelve metals was determined, non of them exceeded the regional background concentrations significantly. The chemical composition of individual particles emitted by the demolition was studied by Scanning Electron Microscopy. They were mainly concrete and steel particles, with 60% calcium carbonates, 19% calcium sulfates, 19% silicates and 2% steel. In energy-dispersive X-Ray Spectroscopy, no fibers like asbestos were observed. Using a broad spectrum of instruments and methods, we obtain comprehensive characterization of the particles emitted by the demolition.
A twentieth century-long coupled atmosphere-ocean regional climate simulation with COSMO-CLM (Consortium for Small-Scale Modeling, Climate Limited-area Model) and NEMO (Nucleus for European Modelling of the Ocean) is studied here to evaluate the added value of coupled marginal seas over continental regions. The interactive coupling of the marginal seas, namely the Mediterranean, the North and the Baltic Seas, to the atmosphere in the European region gives a comprehensive modelling system. It is expected to be able to describe the climatological features of this geographically complex area even more precisely than an atmosphere-only climate model. The investigated variables are precipitation and 2 m temperature. Sensitivity studies are used to assess the impact of SST (sea surface temperature) changes over land areas. The different SST values affect the continental precipitation more than the 2 m temperature. The simulated variables are compared to the CRU (Climatic Research Unit) observational data, and also to the HOAPS/GPCC (Hamburg Ocean Atmosphere Parameters and Fluxes from Satellite Data, Global Precipitation Climatology Centre) data. In the coupled simulation, added skill is found primarily during winter over the eastern part of Europe. Our analysis shows that, over this region, the coupled system is dryer than the uncoupled system, both in terms of precipitation and soil moisture, which means a decrease in the bias of the system. Thus, the coupling improves the simulation of precipitation over the eastern part of Europe, due to cooler SST values and in consequence, drier soil.
We evaluate the near-surface representation of thermally driven winds in the Swiss Alps in a numerical weather prediction model at km-scale resolution. In addition, the influence of grid resolution (2.2 km and 1.1 km), topography filtering, and land surface datasets on the accuracy of the simulated valley winds is investigated. The simulations are evaluated against a comprehensive set of surface observations for an 18-day fair-weather summer period in July 2006. The episode is characterized by strong diurnal wind systems and the formation of shallow convection over the mountains, which transitions to precipitating convection in some areas. The near-surface winds (10 m above ground level) follow a typical diurnal pattern with strong daytime up-valley flow and weaker nighttime down-valley flow. At a 2.2 km resolution the valley winds are poorly simulated for most stations, while at a 1.1 km resolution the diurnal cycle of the valley winds is well represented in most large (e.g., Rhein valley at Chur and Rhone valley at Visp) and medium-sized valleys (e.g., Linth valley at Glarus). In the smaller valleys (e.g., Maggia valley at Cevio), the amplitude of the valley wind is still significantly underestimated, even at a 1.1 km resolution. Detailed sensitivity experiments show that the use of high-resolution land surface datasets, for both the soil characteristics as well as for the land cover, and reduced filtering of the topography are essential to achieve good performance at a 1.1 km resolution
The synthesis of polynitrogen compounds is of fundamental importance due to their potential as environmentally-friendly high energy density materials. Attesting to the intrinsic difficulties related to their formation, only three polynitrogen ions, bulk stabilized as salts, are known. Here, magnesium and molecular nitrogen are compressed to about 50 GPa and laser-heated, producing two chemically simple salts of polynitrogen anions, MgN4 and Mg2N4. Single-crystal X-ray diffraction reveals infinite anionic polythiazyl-like 1D N-N chains in the crystal structure of MgN4 and cis-tetranitrogen N44− units in the two isosymmetric polymorphs of Mg2N4. The cis-tetranitrogen units are found to be recoverable at atmospheric pressure. Our results respond to the quest for polynitrogen entities stable at ambient conditions, reveal the potential of employing high pressures in their synthesis and enrich the nitrogen chemistry through the discovery of other nitrogen species, which provides further possibilities to design improved polynitrogen arrangements.
Abiotic formation of n-alkane hydrocarbons has been postulated to occur within Earth's crust. Apparent evidence was primarily based on uncommon carbon and hydrogen isotope distribution patterns that set methane and its higher chain homologues apart from biotic isotopic compositions associated with microbial production and closed system thermal degradation of organic matter. Here, we present the first global investigation of the carbon and hydrogen isotopic compositions of n-alkanes in volcanic-hydrothermal fluids hosted by basaltic, andesitic, trachytic and rhyolitic rocks. We show that the bulk isotopic compositions of these gases follow trends that are characteristic of high temperature, open system degradation of organic matter. In sediment-free systems, organic matter is supplied by surface waters (seawater, meteoric water) circulating through the reservoir rocks. Our data set strongly implies that thermal degradation of organic matter is able to satisfy isotopic criteria previously classified as being indicative of abiogenesis. Further considering the ubiquitous presence of surface waters in Earth’s crust, abiotic hydrocarbon occurrences might have been significantly overestimated.
Analysis of stratospheric transport from an observational point of view is frequently realized by evaluation of mean age of air values from long-lived trace gases. However, this provides more insight into general transport strength and less into its mechanism. Deriving complete transit time distributions (age spectra) is desirable, but their deduction from direct measurements is difficult and so far primarily achieved by assumptions about dynamics and spectra themselves. This paper introduces a modified version of an inverse method to infer age spectra from mixing ratios of short-lived trace gases. For a full description of transport seasonality the formulation includes an imposed seasonal cycle to gain multimodal spectra. The EMAC model simulation used for a proof of concept features an idealized dataset of 40 radioactive trace gases with different chemical lifetimes as well as 40 chemically inert pulsed trace gases to calculate pulse age spectra. Annual and seasonal mean inverse spectra are compared to pulse spectra including first and second moments as well as the ratio between them to assess the performance on these time scales. Results indicate that the modified inverse age spectra match the annual and seasonal pulse age spectra well on global scale beyond 1.5 years mean age of air. The imposed seasonal cycle emerges as a reliable tool to include transport seasonality in the age spectra. Below 1.5 years mean age of air, tropospheric influence intensifies and breaks the assumption of single entry through the tropical tropopause, leading to inaccurate spectra in particular in the northern hemisphere. The imposed seasonal cycle wrongly prescribes seasonal entry in this lower region and does not lead to a better agreement between inverse and pulse age spectra without further improvement. As the inverse method aims for future implementation on in situ observational data, possible critical factors for this purpose are delineated finally.
Deriving stratospheric age of air spectra using an idealized set of chemically active trace gases
(2019)
Analysis of stratospheric transport from an observational point of view is frequently realized by evaluation of the mean age of air values from long-lived trace gases. However, this provides more insight into general transport strength and less into its mechanism. Deriving complete transit time distributions (age spectra) is desirable, but their deduction from direct measurements is difficult. It is so far primarily based on model work. This paper introduces a modified version of an inverse method to infer age spectra from mixing ratios of short-lived trace gases and investigates its basic principle in an idealized model simulation. For a full description of transport seasonality the method includes an imposed seasonal cycle to gain multimodal spectra. An ECHAM/MESSy Atmospheric Chemistry (EMAC) model simulation is utilized for a general proof of concept of the method and features an idealized dataset of 40 radioactive trace gases with different chemical lifetimes as well as 40 chemically inert pulsed trace gases to calculate pulse age spectra. It is assessed whether the modified inverse method in combination with the seasonal cycle can provide matching age spectra when chemistry is well-known. Annual and seasonal mean inverse spectra are compared to pulse spectra including first and second moments as well as the ratio between them to assess the performance on these timescales. Results indicate that the modified inverse age spectra match the annual and seasonal pulse age spectra well on global scale beyond 1.5 years of mean age of air. The imposed seasonal cycle emerges as a reliable tool to include transport seasonality in the age spectra. Below 1.5 years of mean age of air, tropospheric influence intensifies and breaks the assumption of single entry through the tropical tropopause, leading to inaccurate spectra, in particular in the Northern Hemisphere. The imposed seasonal cycle wrongly prescribes seasonal entry in this lower region and does not lead to a better agreement between inverse and pulse age spectra without further improvement. Tests with a focus on future application to observational data imply that subsets of trace gases with 5 to 10 species are sufficient for deriving well-matching age spectra. These subsets can also compensate for an average uncertainty of up to ±20 % in the knowledge of chemical lifetime if a deviation of circa ±10 % in modal age and amplitude of the resulting spectra is tolerated.