550 Geowissenschaften
Refine
Year of publication
Document Type
- Article (902)
- Doctoral Thesis (194)
- Contribution to a Periodical (32)
- Book (26)
- Working Paper (22)
- Part of Periodical (21)
- Conference Proceeding (18)
- Part of a Book (9)
- Diploma Thesis (8)
- diplomthesis (7)
Language
Keywords
- climate change (11)
- Klima (8)
- Climate change (7)
- Klimaänderung (7)
- Modellierung (7)
- COSMO-CLM (6)
- Klimawandel (6)
- Palaeoclimate (6)
- precipitation (6)
- Atmospheric chemistry (5)
Institute
- Geowissenschaften (778)
- Geowissenschaften / Geographie (144)
- Biodiversität und Klima Forschungszentrum (BiK-F) (62)
- Geographie (61)
- Senckenbergische Naturforschende Gesellschaft (56)
- Präsidium (44)
- Extern (28)
- Biowissenschaften (22)
- Institut für Ökologie, Evolution und Diversität (10)
- Physik (8)
- Institut für sozial-ökologische Forschung (ISOE) (6)
- Frankfurt Institute for Advanced Studies (FIAS) (5)
- Medizin (5)
- SFB 268 (4)
- Geschichtswissenschaften (3)
- Starker Start ins Studium: Qualitätspakt Lehre (3)
- Biochemie und Chemie (2)
- Center for Scientific Computing (CSC) (2)
- Informatik und Mathematik (2)
- Zentrum für Interdisziplinäre Afrikaforschung (ZIAF) (2)
- keine Angabe Institut (2)
- Center for Financial Studies (CFS) (1)
- Fachübergreifend (1)
- Gesellschaftswissenschaften (1)
- House of Finance (HoF) (1)
- Informatik (1)
- Sprach- und Kulturwissenschaften (1)
- Wirtschaftswissenschaften (1)
Samples of freshly fallen snow were collected at the high alpine research station Jungfraujoch (Switzerland) in February and March 2006 and 2007, during the Cloud and Aerosol Characterization Experiments (CLACE) 5 and 6. In this study a new technique has been developed and demonstrated for the measurement of organic acids in fresh snow. The melted snow samples were subjected to solid phase extraction and resulting solutions analysed for organic acids by HPLC-MS-TOF using negative electrospray ionization. A series of linear dicarboxylic acids from C5 to C13 and phthalic acid, were identified and quantified. In several samples the biogenic acid pinonic acid was also observed. In fresh snow the median concentration of the most abundant acid, adipic acid, was 0.69 micro g L -1 in 2006 and 0.70 micro g L -1 in 2007. Glutaric acid was the second most abundant dicarboxylic acid found with median values of 0.46 micro g L -1 in 2006 and 0.61 micro g L -1 in 2007, while the aromatic acid phthalic acid showed a median concentration of 0.34 micro g L -1 in 2006 and 0.45 micro g L -1 in 2007. The concentrations in the samples from various snowfall events varied significantly, and were found to be dependent on the back trajectory of the air mass arriving at Jungfraujoch. Air masses of marine origin showed the lowest concentrations of acids whereas the highest concentrations were measured when the air mass was strongly influenced by boundary layer air.
Samples of freshly fallen snow were collected at the high alpine research station Jungfraujoch (Switzerland) in February and March 2006 and 2007, during the Cloud and Aerosol Characterization Experiments (CLACE) 5 and 6. In this study a new technique has been developed and demonstrated for the measurement of organic acids in fresh snow. The melted snow samples were subjected to solid phase extraction and resulting solution analysed for organic acids by HPLC-MS-TOF using negative electrospray ionization. A series of linear dicarboxylic acids from C5 to C13 and phthalic acid, were identified and quantified. In several samples the biogenic acid pinonic acid was also observed. In fresh snow the median concentration of the most abundant acid, adipic acid, was 0.69 µg L−1 in 2006 and 0.70 µg L−1 in 2007. Glutaric acid was the second most abundant dicarboxylic acid found with median values of 0.46 µg L−1 in 2006 and 0.61 µg L−1 in 2007, while the aromatic acid phthalic acid showed a median concentration of 0.34 µg L−1 in 2006 and 0.45 µg L−1 in 2007. The concentrations in the samples from various snowfall events varied significantly, and were found to be dependent on the back trajectory of the air mass arriving at Jungfraujoch. Air masses of marine origin showed the lowest concentrations of acids whereas the highest concentrations were measured when the air mass was strongly influenced by boundary layer air.
Nichtmethan-Kohlenwasserstoffe sind in Gegenwart von Stickstoffoxiden (NO, NO2) wichtige Vorläufersubstanzen von troposphärischen Photooxidantien (z. B. Ozon), die beim photochemischen Metabolismus gasförmiger organischer Verbindungen durch Hydroxylradikale (OH) unter Einwirkung von Sonnenlicht gebildet werden. Experimenteller Beitrag dieser Arbeit ist die Charakterisierung, Modifizierung, Optimierung und Qualitätssicherung des zur Messung von leichtflüchtigen atmosphärischen C2-C10 Kohlenwasserstoffen verwendeten mobilen Gaschromatographen (GC) mit Flammenionisationsdetektor (AirmoVOC HC2010). Im Rahmen des vom BIvIBF geförderten Berlin Ozonexperiments BERLIOZ, das im Sommer 1998 im Großraum Berlin/Brandenburg stattfand, wurden an einer ländlichen Bodenstation in Blossin, 40 km südöstlich Berlins, in situ Messungen von 69 Nichtmethan-Kohlenwasserstoffen durchgeführt. im Vorfeld der Feldkampagne wurde der GC einer umfangreichen Qualitätssicherung unterzogen. Bei einer Immissionsvergleichsmessung, die unter Beteiligung aller Arbeitsgruppen stattfand, ergab sich eine mittlere konzentrationsabhängige Abweichung des HC-2010 von ± 16% und ein konstanter Offset (Bias) von 0,71 nmol/m3 (16 pptv) vom Referenzmeßverfahren des Forschungszentrums Jülich. Die Geräteblindwerte waren für die meisten Analyten kleiner 0,3 nmol/m3 (6 pptv). Aus der dreifachen Standardabweichung der Blindwerte ergaben sich die für Außenluftuntersuchungen geforderten Nachweisgrenzen um 0,4 nmol/m3 (10 pptv). Im zweiten Teil dieser Arbeit wurde der BERLIOZ-Datensatz hinsichtlich einer Bestandsaufnahme ausgewertet. Die beobachteten Konzentrationen der einzelnen Kohlenwasserstoffe wiesen jeweils eine logarithmische Normalverteilung auf, die Charakterisierung des Datensatzes erfolgte deshalb nicht anhand von arithmetischem Mittelwert und Standardabweichung, sondern mit geometrischem Mittelwert und multiplikativer Standardabweichung. Anhand der OH-Verlustrate wurde der Einfluß der verschiedenen Kohlenwasserstoffe auf die lokale Bildung von Photooxidantien untersucht. Der natürliche Kohlenwasserstoff Isopren lieferte mit 70% den weitaus größten mittleren Beitrag zur Photooxidantienproduktion am Boden. In der Grenzschicht verlor isopren allerdings seine dominante Rolle. Sein Beitrag schrumpfte mit zunehmender Höhe auf 20-40%. in der in 200 m Höhe beobachteten Abluftfahne Berlins verursachten anthropogene Kohlenwasserstoffe rund 2/3 der OH-Verlustrate, wobei die reaktiven C3/C4-Alkene alleine bereits 50% beitrugen.
When studying new particle formation, the uncertainty in determining the "true" nucleation rate is considerably reduced when using condensation particle counters (CPCs) capable of measuring concentrations of aerosol particles at sizes close to or even at the critical cluster size (1–2 nm). Recently, CPCs able to reliably detect particles below 2 nm in size and even close to 1 nm became available. Using these instruments, the corrections needed for calculating nucleation rates are substantially reduced compared to scaling the observed formation rate to the nucleation rate at the critical cluster size. However, this improved instrumentation requires a careful characterization of their cut-off size and the shape of the detection efficiency curve because relatively small shifts in the cut-off size can translate into larger relative errors when measuring particles close to the cut-off size.
Here we describe the development of two continuous-flow CPCs using diethylene glycol (DEG) as the working fluid. The design is based on two TSI 3776 counters. Several sets of measurements to characterize their performance at different temperature settings were carried out. Furthermore, two mixing-type particle size magnifiers (PSM) A09 from Airmodus were characterized in parallel. One PSM was operated at the highest mixing ratio (1 L min−1 saturator flow), and the other was operated in a scanning mode, where the mixing ratios are changed periodically, resulting in a range of cut-off sizes. The mixing ratios are determined by varying the saturator flow, where the aerosol flow stays constant at 2.5 L min−1. Different test aerosols were generated using a nano-differential mobility analyser (nano-DMA) or a high-resolution DMA, to obtain detection efficiency curves for all four CPCs. One calibration setup included a high-resolution mass spectrometer (APi-TOF) for the determination of the chemical composition of the generated clusters. The lowest cut-off sizes were achieved with negatively charged ammonium sulfate clusters, resulting in cut-offs of 1.4 nm for the laminar flow CPCs and 1.2 and 1.1 nm for the PSMs. A comparison of one of the laminar-flow CPCs and one of the PSMs measuring ambient and laboratory air showed good agreement between the instruments.
When studying new particle formation, the uncertainty in determining the "true" nucleation rate is considerably reduced when using Condensation Particle Counters (CPCs) capable of measuring concentrations of aerosol particles at sizes close to or even at the critical cluster size (1–2 nm). Recently CPCs, able to reliably detect particles below 2 nm in size and even close to 1 nm became available. The corrections needed to calculate nucleation rates are substantially reduced compared to scaling the observed formation rate to the nucleation rate at the critical cluster size. However, this improved instrumentation requires a careful characterization of their cut-off size and the shape of the detection efficiency curve because relatively small shifts in the cut-off size can translate into larger relative errors when measuring particles close to the cut-off size.
Here we describe the development of two continuous flow CPCs using diethylene glycol (DEG) as the working fluid. The design is based on two TSI 3776 counters. Several sets of measurements to characterize their performance at different temperature settings were carried out. Furthermore two mixing-type Particle Size Magnifiers (PSM) A09 from Airmodus were characterized in parallel. One PSM was operated at the highest mixing ratio (1 L min−1 saturator flow), and the other was operated in a scanning mode, where the mixing ratios are changed periodically, resulting in a range of cut-off sizes. Different test aerosols were generated using a nano-Differential Mobility Analyzer (nano-DMA) or a high resolution DMA, to obtain detection efficiency curves for all four CPCs. One calibration setup included a high resolution mass spectrometer (APi-TOF) for the determination of the chemical composition of the generated clusters. The lowest cut-off sizes were achieved with negatively charged ammonium sulphate clusters, resulting in cut-offs of 1.4 nm for the laminar flow CPCs and 1.2 and 1.1 nm for the PSMs. A comparison of one of the laminar-flow CPCs and one of the PSMs measuring ambient and laboratory air showed good agreement between the instruments.
Aus einem 815 cm langen Bohrprofil, das AVERDIECK (1.c.) aus den "Grundlosen" bei Höxter (Westfalen) geborgen hatte, wurden aus den oberen 7 m 20 Proben mit Hilfe der Radiokohlenstoff-Methode absolut datiert. Ein Teil der Ablagerungen ergab ein im Vergleich zu den darunterliegenden Schichten zu hohes Alter, was auf die Beimengung allochthonen Materials zurückzuführen ist. Die übrigen 14C-Daten dienen zur zeitlichen Einordnung des von AVERDIECK erstellten Pollendiagramms und zeigen, dass einige Grenzen von Pollenzonen im Wesertal mehrere Jahrhunderte früher liegen als in der Norddeutschen Tiefebene.
We developed a coupled regional climate system model based on the CCLM regional climate model. Within this model system, using OASIS3-MCT as a coupler, CCLM can be coupled to two land surface models (the Community Land Model (CLM) and VEG3D), the NEMO-MED12 regional ocean model for the Mediterranean Sea, two ocean models for the North and Baltic seas (NEMO-NORDIC and TRIMNP+CICE) and the MPI-ESM Earth system model.
We first present the different model components and the unified OASIS3-MCT interface which handles all couplings in a consistent way, minimising the model source code modifications and defining the physical and numerical aspects of the couplings. We also address specific coupling issues like the handling of different domains, multiple usage of the MCT library and exchange of 3-D fields.
We analyse and compare the computational performance of the different couplings based on real-case simulations over Europe. The usage of the LUCIA tool implemented in OASIS3-MCT enables the quantification of the contributions of the coupled components to the overall coupling cost. These individual contributions are (1) cost of the model(s) coupled, (2) direct cost of coupling including horizontal interpolation and communication between the components, (3) load imbalance, (4) cost of different usage of processors by CCLM in coupled and stand-alone mode and (5) residual cost including i.a. CCLM additional computations.
Finally a procedure for finding an optimum processor configuration for each of the couplings was developed considering the time to solution, computing cost and parallel efficiency of the simulation. The optimum configurations are presented for sequential, concurrent and mixed (sequential+concurrent) coupling layouts. The procedure applied can be regarded as independent of the specific coupling layout and coupling details.
We found that the direct cost of coupling, i.e. communications and horizontal interpolation, in OASIS3-MCT remains below 7 % of the CCLM stand-alone cost for all couplings investigated. This is in particular true for the exchange of 450 2-D fields between CCLM and MPI-ESM. We identified remaining limitations in the coupling strategies and discuss possible future improvements of the computational efficiency.
Plant community biomass production is co-dependent on climatic and edaphic factors that are often covarying and non-independent. Disentangling how these factors act in isolation is challenging, especially along large climatic gradients that can mask soil effects. As anthropogenic pressure increasingly alters local climate and soil resource supply unevenly across landscapes, our ability to predict concurrent changes in plant community processes requires clearer understandings of independent and interactive effects of climate and soil. To address this, we developed a multispecies phytometer (i.e., standardized plant community) for separating key drivers underlying plant productivity across gradients. Phytometers were composed of three globally cosmopolitan herbaceous perennials, Dactylis glomerata, Plantago lanceolata, and Trifolium pratense. In 2017, we grew phytometer communities in 18 sites across a pan-European aridity gradient in local site soils and a standardized substrate and compared biomass production. Standard substrate phytometers succeeded in providing a standardized climate biomass response independent of local soil effects. This allowed us to factor out climate effects in local soil phytometers, establishing that nitrogen availability did not predict biomass production, while phosphorus availability exerted a strong, positive effect independent of climate. Additionally, we identified a negative relationship between biomass production and potassium and magnesium availability. Species-specific biomass responses to the environment in the climate-corrected biomass were asynchronous, demonstrating the importance of species interactions in vegetation responses to global change. Biomass production was co-limited by climatic and soil drivers, with each species experiencing its own unique set of co-limitations. Our study demonstrates the potential of phytometers for disentangling effects of climate and soil on plant biomass production and suggests an increasing role of P limitation in the temperate regions of Europe.
The purpose of this study was to reconstruct the depositional environment, the genesis and the composition of Miocene coals in the Kutai Basin, East Kalimantan, Indonesia and to improve our understanding of the factors controlling the organic and inorganic composition, variation of biomarkers, and the peat forming vegetation of the coals. To achieve the aim methods belonging to three different disciplines were applied: 1. Coal petrology (chapter 3) 2. Inorganic geochemistry: sulfur, pyrite and mineral matter distributions (chapter 4) 3. Organic geochemistry of saturated, aromatic hydrocarbon fractions and stable carbon isotopic composition (chapter 5 and 6) Coal petrology Coal developes from peat deposited in mires, mainly in swamps and raised bogs. It is therefore necessary to consider how peat was formed in the past. Coal contains a variety of plant tissues in different degrees of preservation. Tissues of distinct origin are microscopically identifiable and can frequently be related to certain parts of the plant, such as cuticles, woody structures, spores, algal, resin, etc. Together with the particles of less certain origin they are termed macerals which are the petrographic components of coal. During and after deposition of plant remains in sedimentary basins, the organic matter will undergo a sequence of physical, biochemical and chemical changes, which finally results in the formation of coals of increasing rank depending mainly on the temperature influence. The process of coalification begins with practically unaltered plant material and peat, and continues with increasing rank through brown coal, bituminous coal, and finally to anthracite as well as graphite. Coal petrography provides valuable of data of maceral and mineral percentages with reflectance values, which can be used to reconstruct the depositional environment and the coalification processes. In lower rank coals, the material is represented by a group of macerals called huminite, and in bituminous and anthracite coals by a group of macerals called vitrinite. Coal petrography analyses have been carried out on samples from some Miocene coal seams from Kutai Basin. The study has shown that huminite reflectance values of coal samples from ...
Forty two samples of the Late Eocene Kiliran oil shale, Central Sumatra Basin, Indonesia were collected from a 102 m long drill core. Palynofacies and geochemical analyses have been carried out to reconstruct the paleoenvironmental conditions and paleoecology during deposition of the oil shale. Amorphous organic matter (AOM) is very abundant (>76%). B. braunii palynomorph is present (3-16%) as the only autochtonous structured organic matter and generally more abundant in middle part of the profile. The stable carbon isotopic composition of organic matter (δ13C) varies from -27.0 to -30.5‰ and is generally more depleted in middle part of the profile. The ratio of total organic carbon to sulfur (TOC/S), used as salinity indicator, ranges from 2.5 to 15.8 and shows variations along the profile. Relatively less saline environments are observed in the middle part profile. Fungal remains are generally present only in middle part of the profile with distinct peak of abundances. The presence of fungal remains is regarded as an indication for a relatively warmer climate during deposition of middle part of the profile. The warmer climate is thought to influence the establishment of a thermocline, limiting the supply of recycled nutrients to the epilimnion. Consequently, the primary productivity in the Kiliran lake decreased during deposition of the middle part of the profile as indicated by the relatively depleted δ13C and the blooming of B. braunii. The chemocline was also shoaling during deposition of the middle part of the profile according to the higher abundance of isorenieratene derivatives of green sulfur bacteria origin. The warmer climate affected also to increase of water supply and thus less saline environments.
Tectonic subsidence is also thought to be a significant factor for the development of the Kiliran lake. The Zr/Rb ratio, an indicator for grain size, ranges from 0.4 to 1.3 and generally increases upwards along the profile. Three sudden decreases of the ratio are observed, indicating rapid change to finer grain size. These decreases are interpreted to indicate rapid deepening events of the lake due to mainly periodic subsidence. During deposition of lower part of the profile, the subsidence rates might have been relatively higher than sediment and water supply rates, resulting in a higher autochtonous fraction in the oil shale. During deposition of middle part of the profile, the sediment and water supply rates were relatively higher promoting distinct progradational sedimentation. Subsequently, the lake became more shallow and smaller during deposition of the upper part of the profile, leading to a relatively higher terrigenous input to the oil shale.
Norneohop-13(18)-ene and neohop-13(18)-ene derived from methanotrophic bacteria are the dominant hopanoid hydrocarbons. The sum of their concentrations varies from 40.6 to 360.0 μg/g TOC. The δ13C of these compounds are extremely depleted (-45.2 to -50.2‰). The occurrence of abundant bacteria including methanotrophic bacteria was responsible for the recycling of carbon below the chemocline of the lake. The effect of the recycling of carbon is observed by the presence of a concomitant depletion (about 7-9‰) in 13C of some specific biomarkers derived from organisms dwelling in the whole phototrophic zone.
4-Methylsterane and 4-methyldiasterene homologues occur in the oil shale as the predominant biomarkers. The sum of the concentrations of all homologues are about 40.3-1,009.2 μg/g TOC with generally higher values in uppermost and lower parts of the profile. Ca accounts as the predominant element in the oil shale, ranging from 5.0 to 16.7%. This element shows generally parallel variation with the 4-methylsterane homologues along the profile. This suggests that the 4-methylsteranes were derived from biological sources favoring more alkaline and more trophic environments. On the other hand, these compounds were less abundant in middle part of the profile which is consistent with less alkaline and less trophic environments promoting B. braunii to bloom.
The 4-methylsterane homologues are considered to originate from Dinoflagellates. Alternation between Dinoflagellates and B. braunii in Paleogene lake systems due to water chemistry changes are known from previous studies. Moreover, freshwater Dinoflagellates have been frequently reported to occur in the basin depocenters. In the present case, distinct alternation between B. braunii abundances and concentrations of 4-methylsterane homologues along the studied oil shale profile suggest that the 4-methylsterane homologues were derived from freshwater Dinoflagellates although dinosterane is not present in the sediment extracts. Water alkalinity and trophic level changes were most likely responsible for the alternation of Dinoflagellates and B. braunii blooming.
Forty two samples of the Late Eocene Kiliran oil shale, Central Sumatra Basin, Indonesia were collected from a 102 m long drill core. The oil shale core represents the deposition time of about 240.000 years. Palynofacies and geochemical analyses have been carried out to reconstruct the paleoenvironmental conditions and paleoecology during deposition of the oil shale. Amorphous organic matter (AOM) is very abundant (>76%). B. braunii palynomorphs are present (3-16%) as the only autochtonous structured organic matter and generally more abundant in the middle part of the profile. The stable carbon isotopic composition of bulk organic matter (13C) varies from -27.0 to -30.5‰ and is generally more depleted in the middle part of the profile. The ratio of total organic carbon to sulfur (TOC/S), used as salinity indicator, ranges from 2.5 to 15.8 and shows variations along the profile. Slightly less saline environments are observed in the middle part of the profile. Fungal remains are generally present only in this part with a distinct peak of abundance. The presence of fungal remains is regarded as an indication for a relatively warmer climate during deposition of the middle part of the profile. The warmer climate is thought to influence the establishment of a thermocline, limiting the supply of recycled nutrients to epilimnion. Consequently, the primary productivity in the Kiliran lake decreased during deposition of the middle part of the profile as indicated by the relatively depleted 13C values and the blooming of B. braunii. The chemocline was also shoaling during the deposition according to the higher abundance of total isorenieratane and its derivatives originated from green sulfur bacteria dwelling in the photic zone euxinia. The warmer climate is also thought to influence the slightly decrease of water salinity during deposition of the middle part of the profile. The occurrence of B. braunii in Kiliran lake is also recognized from organic geochemical data. The distribution of n-alkanes is characterized by the unusual high amount of C27 n-alkane relative to the other long-chain n-alkanes. The concentrations of C27 n-alkane vary from 30.1 to 393.7 μg/g TOC and are generally in parallel with the abundances of B. braunii palynomorphs along the profile. The 13C values of this compound are about -31‰ and up to 2‰ enriched relative to those of the adjacent long-chain n-alkanes. B. braunii race A can thus be regarded as the significant biological source of the C27 n-alkane. Lower amounts of lycopane are observed in many oil shale samples (0 to 54.7 μg/g TOC). The 13C value of this compound is 17.2‰. This strong enrichment of 13C suggests that the lycopane was derived from B. braunii race L. The concentrations of lycopane develop generally in opposite with those of C27 μalkane. It is likely that both B. braunii races bloomed in alternation in the lake, probably due to changes on specific water chemistry. Norneohop-13(18)-ene and neohop-13(18)-ene derived from methanotrophic bacteria are the dominant hopanoid hydrocarbons. The sum of their concentrations varies from 40.6 to 360.0 μg/g TOC. The 13C of these compounds are extremely depleted (-45.2 to -50.2‰). The occurrence of abundant bacteria including methanotrophic bacteria was responsible for the recycling of carbon below the chemocline of the lake. The effect of the recycling of carbon is observed by the presence of a concomitant depletion (about 7-9‰) in 13C of some specific biomarkers derived from organisms dwelling in the whole phototrophic zone. 4-Methylsterane and 4-methyldiasterene homologues occur in the oil shale as the predominant biomarkers. The sum of the concentrations of all homologues are about 40.3-1,009.2 μg/g TOC with generally higher values in the uppermost and lower parts of the profile. Calcium (Ca) accounts as the predominant element in the oil shale, ranging from 5.0 to 16.7%. This element shows generally parallel variation with the 4-methylsterane and 4-methyldiasterene homologues along the profile. This suggests that these compounds were derived from biological sources favoring more alkaline and more trophic environments. On the other hand, these compounds were less abundant in the middle part of the profile which is consistent with less alkaline and less trophic environments promoting B. braunii to bloom. Alternation between Dinoflagellates and B. braunii in ancient lacustrine environments due to water chemistry changes have been known from previous studies. In the present case, distinct alternation between B. braunii abundances and concentrations of 4-methylsterane and 4-methyldiasterene homologues along the studied oil shale profile suggest a hypothesis that these compounds were derived from freshwater Dinoflagellates although dinosterane is not present in the sediment extracts. Water alkalinity and trophic level changes were most likely responsible for the alternation of Dinoflagellates and B. braunii blooming.
Seven different instruments and measurement methods were used to examine the immersion freezing of bacterial ice nuclei from Snomax® (hereafter Snomax), a product containing ice active protein complexes from non-viable Pseudomonas syringae bacteria. The experimental conditions were kept as similar as possible for the different measurements. Of the participating instruments, some examined droplets which had been made from suspensions directly, and the others examined droplets activated on previously generated Snomax particles, with particle diameters of mostly a few hundred nanometers and up to a few micrometers in some cases. Data were obtained in the temperature range from −2 to −38 °C, and it was found that all ice active protein complexes were already activated above −12 °C. Droplets with different Snomax mass concentrations covering 10 orders of magnitude were examined. Some instruments had very short ice nucleation times down to below 1 s, while others had comparably slow cooling rates around 1 K min−1. Displaying data from the different instruments in terms of numbers of ice active protein complexes per dry mass of Snomax, nm, showed that within their uncertainty the data agree well with each other as well as to previously reported literature results. Two parameterizations were taken from literature for a direct comparison to our results, and these were a time dependent approach based on a contact angle distribution Niedermeier et al. (2014) and a modification of the parameterization presented in Hartmann et~al.~(2013) representing a time independent approach. The agreement between these and the measured data were good, i.e. they agreed within a temperature range of 0.6 K or equivalently a range in nm of a factor of 2. From the results presented herein, we propose that Snomax, at least when carefully shared and prepared, is a suitable material to test and compare different instruments for their accuracy of measuring immersion freezing.
Seven different instruments and measurement methods were used to examine the immersion freezing of bacterial ice nuclei from Snomax® (hereafter Snomax), a product containing ice-active protein complexes from non-viable Pseudomonas syringae bacteria. The experimental conditions were kept as similar as possible for the different measurements. Of the participating instruments, some examined droplets which had been made from suspensions directly, and the others examined droplets activated on previously generated Snomax particles, with particle diameters of mostly a few hundred nanometers and up to a few micrometers in some cases. Data were obtained in the temperature range from −2 to −38 °C, and it was found that all ice-active protein complexes were already activated above −12 °C. Droplets with different Snomax mass concentrations covering 10 orders of magnitude were examined. Some instruments had very short ice nucleation times down to below 1 s, while others had comparably slow cooling rates around 1 K min−1. Displaying data from the different instruments in terms of numbers of ice-active protein complexes per dry mass of Snomax, nm, showed that within their uncertainty, the data agree well with each other as well as to previously reported literature results. Two parameterizations were taken from literature for a direct comparison to our results, and these were a time-dependent approach based on a contact angle distribution (Niedermeier et al., 2014) and a modification of the parameterization presented in Hartmann et al. (2013) representing a time-independent approach. The agreement between these and the measured data were good; i.e., they agreed within a temperature range of 0.6 K or equivalently a range in nm of a factor of 2. From the results presented herein, we propose that Snomax, at least when carefully shared and prepared, is a suitable material to test and compare different instruments for their accuracy of measuring immersion freezing.
Active chlorine species play a dominant role in the catalytic destruction of stratospheric ozone in the polar vortices during the late winter and early spring seasons. Recently, the correct understanding of the ClO dimer cycle was challenged by the release of new laboratory absorption cross sections (Pope et al., 2007) yielding significant model underestimates of observed ClO and ozone loss (von Hobe et al., 2007). Under this aspect, Arctic stratospheric limb emission measurements carried out by the balloon version of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS-B) from Kiruna (Sweden) on 11 January 2001 and 20/21 March 2003 have been reanalyzed with regard to the chlorine reservoir species ClONO2 and the active species, ClO and ClOOCl (Cl2O2). New laboratory measurements of IR absorption cross sections of ClOOCl for various temperatures and pressures allowed for the first time the retrieval of ClOOCl mixing ratios from remote sensing measurements. High values of active chlorine (ClOx) of roughly 2.3 ppbv at 20 km were observed by MIPAS-B in the cold mid-winter Arctic vortex on 11 January 2001. While nighttime ClOOCl shows enhanced values of nearly 1.1 ppbv at 20 km, ClONO2 mixing ratios are less than 0.1 ppbv at this altitude. In contrast, high ClONO2 mixing ratios of nearly 2.4 ppbv at 20 km have been observed in the late winter Arctic vortex on 20 March 2003. No significant ClOx amounts are detectable on this date since most of the active chlorine has already recovered to its main reservoir species ClONO2. The observed values of ClOx and ClONO2 are in line with the established chlorine chemistry. The thermal equilibrium constants between the dimer formation and its dissociation, as derived from the balloon measurements, are on the lower side of reported data and in good agreement with values recommended by von Hobe et al. (2007). Calculations with the ECHAM/MESSy Atmospheric Chemistry model (EMAC) using established kinetics show similar chlorine activation and deactivation, compared to the measurements in January 2001 and March 2003, respectively.
Active chlorine species play a dominant role in the catalytic destruction of stratospheric ozone in the polar vortices during the late winter and early spring seasons. Recently, the correct understanding of the ClO dimer cycle was challenged by the release of new laboratory absorption cross sections (Pope et al., 2007) yielding significant model underestimates of observed ClO and ozone loss (von Hobe et al., 2007). Under this aspect, nocturnal Arctic stratospheric limb emission measurements carried out by the balloon version of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS-B) from Kiruna (Sweden) on 11 January 2001 and 20/21 March 2003 have been reanalyzed with regard to the chlorine reservoir species ClONO2 and the active species, ClO and ClOOCl (Cl2O2). New laboratory measurements of IR absorption cross sections of ClOOCl for various temperatures and pressures allowed for the first time the retrieval of ClOOCl mixing ratios from remote sensing measurements. High values of active chlorine (ClOx) of roughly 2.3 ppbv at 20 km were observed by MIPAS-B in the cold mid-winter Arctic vortex on 11 January 2001. While nighttime ClOOCl shows enhanced values of nearly 1.1 ppbv at 20 km, ClONO2 mixing ratios are less than 0.1 ppbv at this altitude. In contrast, high ClONO2 mixing ratios of nearly 2.4 ppbv at 20 km have been observed in the late winter Arctic vortex on 20 March 2003. No significant ClOx amounts are detectable on this date since most of the active chlorine has already recovered to its main reservoir species ClONO2. The observed values of ClOx and ClONO2 are in line with the established polar chlorine chemistry. The thermal equilibrium constants between the dimer formation and its dissociation, as derived from the balloon measurements, are on the lower side of reported data and in good agreement with values recommended by von Hobe et al. (2007). Calculations with the ECHAM/MESSy Atmospheric Chemistry model (EMAC) using established kinetics show similar chlorine activation and deactivation, compared to the measurements in January 2001 and March 2003, respectively.
Die Chemie und der Strahlungshaushalt der Erdatmosphäre werden durch die nur in relativ geringen Konzentrationen vorhandenen Spurengase und Aerosolpartikel beherrscht. Mit den zunehmenden anthropogenen Emissionen von atmosphärischen Spurengasen, verursacht durch die wachsende Weltbevölkerung und die zunehmende Industrialisierung, wurde in den letzten Dekaden ein globaler Wandel bei der Zusammensetzung der Erdatmosphäre festgestellt: Konzentrationen von atmosphärischen Spurenstoffen verändern sich nicht mehr auf vergleichsweise langsamen geologischen Zeitskalen, sondern mit viel höheren Geschwindigkeiten, in einzelnen Fällen von bis zu einem Prozent pro Jahr. Die wohl bekanntesten Folgen dieser Veränderungen sind die globale Erwärmung durch die ansteigenden Emissionen von Treibhausgasen und der mit dem antarktischen 'Ozonloch" entdeckte drastische Ozonverlust in der Stratosphäre durch anthropogene Fluor-Chlor-Kohlenwasserstoffe (FCKW). Die Verteilung der für Ozonchemie und Klima relevanten Spurengase in der Atmosphäre hängt dabei nicht nur von der Verteilung ihrer Quellen und Senken ab, sondern wird maßgeblich durch verschiedene Transportprozesse beeinflußt. Der Austausch zwischen der mit anthropogenen Emissionen belasteten Troposphäre und den höheren Atmosphärenschichten Stratosphäre und Mesosphäre spielt dabei eine zentrale Rolle. Im Rahmen der Dissertation wurde zum besseren Verständnis von Stratosphären-Troposphären-Austauschprozessen die Verteilung von langlebigen Spurengasen in den beiden atmosphärischen Kompartimenten Troposphäre und Stratosphäre untersucht. Dazu wurde bei einer Meßkampagne im Sommer 1998 im Rahmen des von der Europäischen Union geförderten Forschungsprojektes STREAM 98 der flugzeuggetragene Gaschromatograph GhOST (Gas chromatograph for the Observation of Stratospheric Tracers) an Bord einer Cessna Citation II der TU Delft in Höhen bis 13 km eingesetzt. Dabei konnten bei zwanzig Meß- und Transferflügen über Kanada, dem Atlantik und Westeuropa umfangreiche Messungen der langlebigen Spurengase N20, F11 und F12 in der oberen Troposphäre und der Untersten Stratosphäre durchgeführt werden. Unter Flugbedingungen wurde mit GhOST während der Kampagne eine Reproduzierbarkeit (1 o) von besser als 0,6 % und eine absolute Genauigkeit von besser als 2 % für alle nachgewiesenen Spurengase erreicht. Diese hohe Meßpräzision konnte durch zahlreiche Vergleichsmessungen mit anderen Meßgeräten und Meßverfahren - im Flugbetrieb und im Labor sichergestellt werden; die Linearität des Geräts wurde zudem mit Hilfe einer barometrisch hergestellten Verdünnungsreihe untersucht. Die mit GhOST bei STREAM 98 gewonnenen Meßwerte wurden zusammen mit Messungen und Modelldaten der am Projekt beteiligten Arbeitsgruppen zur Untersuchung von Spurengasverteilungen und Stratosphären-Troposphären-Austauschprozessen herangezogen. Untersucht wurden dabei unter anderem die Verteilung und Variabilität von N20, F11 und F12 in der Troposphäre und in der Untersten Stratosphäre der mittleren Breiten, Austausch- und Mischungsprozesse in der Tropopausenregion und die Variabilität von Tracer/Tracer-Korrelationen in der Untersten Stratosphäre. Aufbauend auf den Erfahrungen bei STREAM 98 wurde für das vom BMBF geförderte Projekt SPURT im Rahmen dieser Doktorarbeit der in-situ-Gaschromatograph GhOST II entwickelt. Unter Beibehaltung der gaschromatographischen Komponenten von GhOST wurden zur Messung der Spurengase SF6 und CO zwei zusätzliche Detektoren integriert und zahlreiche technische Verbesserungen durchgeführt. Für die vollautomatische rechnergestützte Elektronik zur Steuerung des neuen Gerätes wurden zusammen mit der institutseigenen Elektronikwerkstatt verschiedene Baugruppen zur Signalführung und -verarbeitung, zur Temperaturmessung und zur Ansteuerung von Leistungskomponenten entwickelt. Während einer Testkampagne im April 2001 wurde GhOST II erfolgreich mechanisch und elektrisch auf einem Learjet 35A integriert und kam bei zwei Meßflügen der Meßkampagne SPURT 1 im November 2001 zum Einsatz.
Das 1913 auf dem Gipfel des Kleinen Feldbergs gegründete Taunus-Observatorium (T.O.) ist eine Einrichtung der Johann Wolfgang Goethe-Universität Frankfurt am Main. Es dient dem Institut für Meteorologie und Geophysik als Forschungsstätte für kontinuierliche Messungen und als Standort für Meßkampagnen in Zusammenarbeit mit anderen Instituten, wie z. B. beim The Kleiner Feldberg Cloud Experiment 1990 [Fuzzi, 1995]. Darüber hinaus wird das Observatorium mit seinen Einrichtungen immer wieder für Messungen im Rahmen von Diplom- und Doktorarbeiten genutzt. Primäres Ziel dieser Diplomarbeit war eine Charakterisierung der zeitlichen Variabilität der luftchemischen Bedingungen am Taunus-Observatorium in Abhängigkeit von Wetter und Witterung. In der Zeit vom 13. Dezember 1996 bis zum 26. März 1997 wurden am Taunus- Observatorium auf dem Kleinen Feldberg mit Hilfe eines gaschromatographischen Analyseverfahrens die Spurengase Kohlenmonoxid und molekularer Wasserstoff gemessen, um die zeitliche Variabilität der luftchemischen Bedingungen am Taunus-Observatorium in Abhängigkeit von Wetter und Witterung zu untersuchen. Bei der Meßreihe am Taunus-Observatorium zeigte sich, daß die zeitlichen Variationen der langlebigen Spurengase CO und H2 über Tage und Wochen maßgeblich durch den Ferntransport von Luftmassen und die jeweilige Großwetterlage bestimmt werden. Mit Hilfe von Trajektorienanalysen konnte gezeigt werden, daß die Messungen stark von Herkunft und Zugweg der jeweiligen Luftmassen abhängen. Deutliche Änderungen der mittleren CO- und H2-Mischungsverhältnisse wurden bei Luftmassenänderungen beobachtet, wie z. B. eine markante Abnahme von Kohlenmonoxid und molekularem Wasserstoff nach dem Durchgang von Kalt- oder Warmfronten. Extreme Unterschiede der gemessenen Spurengaskonzentrationen konnten auch bei verschiedenen winterlichen Inversionswetterlagen registriert werden. Befand sich das Taunus-Observatorium unterhalb einer Temperaturinversion in der bodennahen Grenzschicht, wurden ungewöhnlich hohe CO- und H2-Mischungsverhältnisse gemessen; war der Kleine Feldberg dagegen über der Inversion innerhalb der freien Atmosphäre, wurden wiederholtdie atmosphärischen Hintergrundkonzentrationen von Kohlenmonoxid und molekularem Wasserstoff beobachtet. Auch durch lokale und regionale Effekte konnten in Abhängigkeit von der lokalen Windrichtung starke zeitliche Variationen der luftchemischen Bedingungen beobachtet werden. Durch die Orographie bedingt Verursachen kleine Änderungen der lokalen Windrichtung drastische Veränderungen in den gemessenen Spurengaskonzentrationen. So trennt z. B. der Taunuskamm die durch regionale Quellen im Großraum Frankfurt belastete Luft im Vordertaunus von der weniger verschmutzter Luft im ländlichen Hintertaunus. Darüber hinaus kann durch die Kanalisierung des Windes in verschiedenen Tälern oder an den Flanken des Taunuskammskontaminierte Luft aus den Niederungen herangeführt werden. Die hohe Variabilität der gemessenen Mischungsverhältnisse in Abhängigkeit von Meteorologie und Orographie dominiert den Tagesverlauf der CO- und H2-Messungen. Daher war eine Untersuchung von anthropogenen Tages- und Wochengängen oder sogar jahreszeitlicher Variationen der langlebigen Spurengase CO und H2 am Taunus-Observatorium nicht möglich. Zusätzlich zu den Messungen am Taunus-Observatorium wurde mit der in dieser Arbeit vorbereiteten Analytik das Mischungsverhältnis von molekularem Wasserstoff in stratosphärischen Luftproben von drei verschiedenen Ballonflügen gemessen, entsprechende H2-Vertikalprofile erstellt und die Ergebnisse der Messungen mit Modellrechnungen verglichen.
This PhD thesis has been carried out within an interdisciplinary cooperational project between the Deutsches Bergbau-Museum Bochum and the Goethe-Universität Frankfurt, which is dedicated to ancient Pb-Ag mining and metal production in the hinterland of the municipium Ulpiana in central Kosovo. Geochemical analysis (OM, XRD, EMP, MC-ICP-MS) of ores, metallurgical (by-) products and metal artefacts allowed to reconstruct the local chaîne opératoire and to decipher significant chronological differences between presumably Roman/late antique and medieval/early modern metallurgical processing. Pb isotope provenance studies documented the relevance of local metal production within the Roman Empire and confirmed the actual existence of a Metalla Dardanica district, which until now solely has been suspected on basis of epigraphy.
The predominant abundance of the by-products matte (Cu, Pb, Fe and Zn sulphides) and speiss (ferrous speiss: Fe-As compounds; base metal speiss: ~(Cu,Ni,Fe,Ag )x(Sb,Sn,As )y ) at smelting sites with a preliminary Roman/late antique dating points to treatment of complex polymetallic ore. Pb isotope analysis demonstrated that the mining district of Shashkoc-Janjevo (partially) supplied six of the ten investigated metallurgical sites. In this mineralisation, parageneses with elevated Cu, As and Sb abundances comprise significant proportions of particularly tennantite-tetrahedrite minerals, chalcopyrite, arsenopyrite and were generated during the early and main stages of ore formation. Later precipitated ore in contrast is marked by a significantly less versatile mineralogy and consists almost exclusively of galena, sphalerite and pyrite/marcasite. Besides increased Cu, As and Sb contents, ore from the main formation stage also exhibits generally higher Ag abundances, which are mainly hosted by fahlore and locally abundant secondary Cu sulphides (chalcocite, digenite and covellite) and oxidised phases (e.g. malachite, azurite). The higher precious metal grades of this ore type, whose geochemical signature (i.e. higher proportions of Cu, As and Sb) is mirrored by the abundance of the metallurgical by-products matte and speiss (almost exclusively found at potentially Roman/late antique smelting sites; see above), presumably were a pivotal factor leading to its preferential exploitation in earlier times. Matte and base metal-rich speiss contain notable amounts of Ag, which are mainly present in Cu-(Fe) sulphides and particularly antimonides ((Cu,Ni)2Sb, Ag3Sb), respectively. While the speiss compounds due to their close association with Pb bullion presumably were cupelled automatically, the metallurgical treatment of matte could not have been proven unambiguously, but overall certainly is highly likely.
The beneficiated ore (i.e. crushed and sorted, potentially also treated by more lavish techniques such as grinding, sieving or wet-mechanical methods) possibly was partially roasted and subsequently together with fluxes and charcoal submitted to the furnaces. The working temperatures approximately ranged between 1100 and 1400 °C. Slags from all presumably Roman/late antique dated and few of their potentially medieval/early modern analogues were produced from smelting of (partially roasted) ore with charcoal and added siliceous material, thus resulting in fayalite-dominant phase assemblages or rarely observed glassy parageneses. Even though several subtypes of fayalite slags have been established on basis of the abundance of Fe-rich oxide phases (i.e. spinel ss and wüstite), late clinopyroxene and the general solidification sequence of the slags, the process conditions (i.e. temperature, fO2, added fluxing agents) must have been widely similar; chemical variations could be explained by varying degrees of interaction of the slag melt with charcoal ash and furnace material. The other investigated metallurgical remains indicate employment of a calcareous flux, which led to formation of Ca-rich olivine-, olivine+clinopyroxene-, clinopyroxene- or melilite-type slags. These types as well as glassy slags were generated at more oxidising conditions outside the fayalite stability field (FMQ buffer equilibrium, cf. Lindsley, 1976) than their olivine-dominant analogues. Conclusions on the furnace construction could be drawn on basis of the typology of the slags, which mostly were tapped into a basin located outside the furnace, but partially (at two presumably medieval/early modern sites) also accumulated in a reservoir within the smelter.
Lead artefacts excavated in Ulpiana could be isotopically related to ores from mineralisations in its vicinity and demonstrate that the resources were at least utilised for local metal production. However, also ship wreck cargo from Israel - including several lead ingots with the inscription 'MET DARD' (Raban, 1999) - and late antique lead-glazed pottery from Serbia and Romania (Walton & Tite, 2010) could be related to a possible Kosovarian/Serbian provenance of the raw material and thus indicate flourishing trade of metal from the Metalla Dardanica district within the Roman Empire.
References:
Lindsley, D. H. (1976). Experimental studies of oxide minerals. In D. Rumble, III (Hrsg.), Oxide minerals (61-88). Reviews in Mineralogy, Volume 3. Washington, DC: Mineralogical Society of America.
Raban, A. (1999). The lead ingots from the wreck site (area K8). Journal of Roman Archaeology, Supplementary Series, 35, 179-188.
Walton, M. S., & Tite, M. S. (2010). Production technology of Roman lead-glazed pottery and its continuance into late antiquity. Archaeometry, 52(5), 733-759.
Strong seasonal variability of hygric and thermal soil conditions are a defining environmental feature in northern Australia. However, how such changes affect the soil–atmosphere exchange of nitrous oxide (N2O), nitric oxide (NO) and dinitrogen (N2) is still not well explored. By incubating intact soil cores from four sites (three savanna, one pasture) under controlled soil temperatures (ST) and soil moisture (SM) we investigated the release of the trace gas fluxes of N2O, NO and carbon dioxide (CO2). Furthermore, the release of N2 due to denitrification was measured using the helium gas flow soil core technique. Under dry pre-incubation conditions NO and N2O emissions were very low (<7.0 ± 5.0 μg NO-N m−2 h−1; <0.0 ± 1.4 μg N2O-N m−2 h−1) or in the case of N2O, even a net soil uptake was observed. Substantial NO (max: 306.5 μg N m−2 h−1) and relatively small N2O pulse emissions (max: 5.8 ± 5.0 μg N m−2 h−1) were recorded following soil wetting, but these pulses were short lived, lasting only up to 3 days. The total atmospheric loss of nitrogen was generally dominated by N2 emissions (82.4–99.3% of total N lost), although NO emissions contributed almost 43.2% to the total atmospheric nitrogen loss at 50% SM and 30 °C ST incubation settings (the contribution of N2 at these soil conditions was only 53.2%). N2O emissions were systematically higher for 3 of 12 sample locations, which indicates substantial spatial variability at site level, but on average soils acted as weak N2O sources or even sinks. By using a conservative upscale approach we estimate total annual emissions from savanna soils to average 0.12 kg N ha−1 yr−1 (N2O), 0.68 kg N ha−1 yr−1 (NO) and 6.65 kg N ha−1 yr−1 (N2). The analysis of long-term SM and ST records makes it clear that extreme soil saturation that can lead to high N2O and N2 emissions only occurs a few days per year and thus has little impact on the annual total. The potential contribution of nitrogen released due to pulse events compared to the total annual emissions was found to be of importance for NO emissions (contribution to total: 5–22%), but not for N2O emissions. Our results indicate that the total gaseous release of nitrogen from these soils is low and clearly dominated by loss in the form of inert nitrogen. Effects of seasonally varying soil temperature and moisture were detected, but were found to be low due to the small amounts of available nitrogen in the soils (total nitrogen <0.1%).
Strong seasonal variability of hygric and thermal soil conditions are a defining environmental feature in Northern Australia. However, how such changes affect the soil–atmosphere exchange of nitrous oxide (N2O), nitric oxide (NO) and dinitrogen (N2) is still 5 not well explored. By incubating intact soil cores from four sites (3 savanna, 1 pasture) under controlled soil temperatures (ST) and soil moisture (SM) we investigated the release of the trace gas fluxes of N2O, NO and carbon dioxide (CO2). Furthermore, the release of N2 due to denitrification was measured using the helium gas flow soil core technique. Under dry pre-incubation conditions NO and N2O emission were very low (< 7.0± 5.0 μgNO-Nm−2 h−1; < 0.0± 1.4 μgN2O-Nm−2 h−1) or in case of N2O, even a net soil uptake was observed. Substantial NO (max: 306.5 μgNm−2 h−1) and relatively small N2O pulse emissions (max: 5.8±5.0 μgNm−2 h−1) were recorded following soil wetting, but these pulses were short-lived, lasting only up to 3 days. The total atmospheric loss of nitrogen was dominated by N2 emissions (82.4–99.3% of total N lost), although NO emissions contributed almost 43.2% at 50% SM and 30 °C ST. N2O emissions were systematically higher for 3 of 12 sample locations, which indicates substantial spatial variability at site level, but on average soils acted as weak N2O sources or even sinks. Emissions were controlled by SM and ST for N2O and CO2, ST and pH for NO, and SM and pH for N2.
Hauptanliegen dieser Arbeit ist es, statistische Zusammenhänge zwischen der Nord-Atlantik-Oszillation (NAO) und der bodennahen Lufttemperatur in Europa zu untersuchen. Dazu wurden zunächst die Korrelationskoeffizienten nach Pearson, Kendall, Spearman und die Transinformation berechnet, sowie die zugehörigen Signifikanzen abgeschätzt. Diese Analysen wurden auch zeitlich gleitend durchgeführt, um mögliche Veränderungen im Einfluß der NAO auf die Temperatur nachweisen zu können. Weiterhin wurde mit Hilfe der selektiven Zeitreihenzerlegung nach signifikanten, charakteristischen zeitlichen Strukturen sowohl in der NAO als auch in den Zeitreihen der Lufttemperatur gesucht: Trend, glatte, saisonale, harmonische Komponente und Rauschen. Zweck dieser Untersuchung war es, gegebenenfalls gleichartige zeitliche Strukturen in der NAO und Temperatur zu finden, um den Zusammenhang zwischen NAO und Temperatur näher beschreiben zu können. Die Untersuchungen wurden fur den Zeitraum von 1871 bis 1990 in monatlicher, saisonaler und jährlicher Auflösung auf Basis von Zeitreihen der mittleren monatlichen Lufttemperatur 41 europäischer WMO- (World Meteorological Organization) Stationen, sowie zwei unterschiedlich definierten NAO-Index-Zeitreihen, die ebenfalls in Monatsmitteln vorlagen, durchgeführt. Ergänzend wurde auf einen globalen Datensatz von Temperaturflächenmitteln zuruckgegriffen, um auch aus globaler Sicht Aussagen uber Zusammenhänge zwischen NAO und bodennaher Lufttemperatur zu erhalten. Die Untersuchungen bezogen sich hierbei auf das Zeitintervall von 1892 bis 1994. Der Zusammenhang zwischen den in Europa beobachteten Temperaturen und der NAO ist linearer Natur und vor allem in den Wintermonaten ausgeprägt. Ein maximaler Zusammenhang findet sich im nordeuropäischen Winter mit einer erklärten Varianz um 40%. Ein Vergleich von extrem kalten Wintern mit der NAO hat gezeigt, daß extreme Kältereignisse nur bei einer schwachen NAO (negativer NAO-Index) auftreten. Im Jahresgang findet eine Verschiebung des durch die NAO beeinflußten Gebietes in Ost-West-Richtung statt. Das Minimum des Zusammenhanges besteht im Sommer bei maximaler Ost-Verschiebung. Weiterhin ist der Einfluß der NAO auf die Temperatur stark zonal ausgeprägt. Es besteht ein Nord-Süd-Gefälle von positiver Korrelation im Norden zu negativer im Süden Europas. Zu diesem Ergebnis führte sowohl die Analyse der Europadaten wie des globalen Datensatzes. Der Einfluß der NAO auf die Temperatur ist nicht stationär; seit Beginn dieses Jahrhunderts hat sich dieser zunehmend ostwärts verlagert. Ein signifikanter Trend konnte in den Indexreihen der NAO aber nicht nachgewiesen werden. Signifikante zeitliche Strukturen der NAO konnten im Bereich der niederfrequenten und auch hochfrequenten Variabilität gefunden werden. Die Winter-NAO (mittlerer Indexwert von Dezember bis Februar) zeigt insbesondere einen in den Wintertemperaturen (Temperaturmittel der Monate Dezember bis Februar) gleichartigen niederfrequenten Verlauf, der durch Polynome vierter und fünfter Ordnung beschrieben werden kann. Im Bereich der hochfrequenten Variabilität konnte mit Ausnahme der Sommer- und Herbstdaten in allen Indexreihen der NAO eine harmonische Schwingung mit einer Periode von etwa 7 Jahren detektiert werden. Die gleiche Schwingung findet sich in den Wintertemperaturen West- und Mitteleuropas.
Since the discovery of the ozone hole [Farman et al., 1985], the dynamics of the stratosphere and the transport of anthropogenic trace gases from the surface to the higher atmosphere has come into the focus of interest. In the tropics, air rises high into the stratosphere and is transported poleward. Trace gases like the CFCs1, photochemically stable in the troposphere, are thus transported into regions where they are photolyzed. The products of the photolysis reactions (eg. Cl, Br) interact in the catalytic ozone cycles and lead to enhanced ozone depletion. Regarding the transport of trace gases, the so-called lowermost stratosphere (LMS) is a very interesting region, where the troposphere and the stratosphere directly interact and air masses out of both regions are mixed. It is the lowest part of the stratosphere between the tropopause and the 380 K isentrope. Tropospheric air can enter this region directly via isentropic transport across the extra-tropical tropopause whereas stratospheric air descends across the 380 K isentrope via the mean meridional circulation. Stratosphere-troposphere exchange (STE) controls the chemical composition of the LMS as well as of the tropopause region and thus has an important effect on the radiative and chemical balance of these regions and the climate system. STE exhibits a strong seasonality [Holton et al., 1995]. While downwelling of stratospheric air across the 380 K isentrope is the dominant process in winter, troposphere-to-stratosphere transport (TST) gains importance in summer, when the downwelling from the stratosphere is only weak. Isentropic transport across the extra-tropical tropopause occurs in regions where the tropopause is strongly disturbed and is connected to tropopause folds, streamer events, frontal zones, polar and subtropical jets, warm conveyor belts and cut-off low systems. A short introduction into STE, the LMS region, and methods to study atmospheric transport is given in Chapter 1. One useful tool to analyse the motions of air and transport processes are longlived trace gases. Since the lifetimes of these tracers are longer than the time scale of the transport processes they are involved in, the distribution of tracers in the atmosphere is mostly determined by dynamics. In the context of this thesis, measurements of such long-lived tracers were performed and used to study transport into the LMS region in the northern hemisphere. During the Vintersol/EuPLEx and ENVISAT validation campaigns in winter 2003, long-lived tracers such as N2O, CH4, CFC-12, CFC-11, H-1211, H2, SF6 and CO2 were measured with the High Altitude Gas Analyser (HAGAR), a two channel in-situ gas chromatograph combined with a CO2 instrument, based on nondispersive infrared absorption. Combined with measurements taken during campaigns in Forli/Italy (ENVISAT validation) in July and October 2002, tracer data were gathered from the tropopause up to altitudes around 20 km during 25 flights on board the Russian high-altitude aircraft M55 Geophysica. Thus, a substantial set of high quality tracer data has been obtained covering the polar vortex region as well as the mid latitudes of the northern hemisphere. Chapter 2 gives an overview of the HAGAR instrument and necessary improvements of the instrumental set up (implementing a CH4 channel) that were performed in the context of this thesis, and review data processing, the measurement campaigns. In order to study transport into the LMS it is assumed that air basically enters the LMS via three different pathways: a) quasi-isentropic transport from the troposphere, b) downward advection from the middle stratosphere through the 380 K surface and c) in the polar vortex region subsidence of air from of the polar vortex. Fractions of air originating in each of these source regions are determined with a simple mass balance calculation by using observations of a subset of the above species with distinct lifetimes (N2O, CH4, CFC-11, H-1211, H2 and O3) yielding complementary constraints on transport from each region. Details of the mass balance calculation and the results are presented in Chapter 3. During the mid-latitude measurement campaigns in Forlí the passing of a cut-off low system associated with an elongated streamer over Europe was observed. The impacts of this event on the trace gas mixing ratios in the LMS are examined in Chapter 4. Finally, a summary is given in Chapter 5.
In this dissertation, different aspects of turbulent transport and thermally driven flows over complex terrain are investigated. Two publications concentrate on the vertical heat and moisture exchange in the convective boundary layer over mountainous terrain. To study this, Large-Eddy Simulation (LES) is used. Both turbulent and advective transport mechanisms are evaluated over the simple orography of a quasi-two-dimensional, periodic valley with prescribed surface fluxes. Here, terrain elevation varies along only one of the horizontal coordinate axes. Even a relatively shallow orography, possibly unresolved in existing numerical weather prediction models, modifies the domain-averaged moisture and temperature profiles. For the analysis, the flow is decomposed into a local turbulent part, a local mean circulation, and a large-scale part. An analysis of the turbulent kinetic energy and turbulent heat and moisture flux budgets shows that the thermal circulation significantly contributes to the vertical transport. It is found that thermal upslope winds are important for the moisture transport from the valley to the mountain tops. In total, moisture export out of the valley is mostly accomplished by the mean circulation. On the temperature distribution, which is horizontally relatively homogeneous, the thermal circulation has a weaker impact. If an upper-level wind is present, it interacts with the thermal circulation. This weakens the vertical transport of moisture and thus reduces its export out of the valley. The heat transport is less affected by the upper-level wind because of its weaker dependence on the thermal circulation. These findings were corroborated in a more realistic experiment simulating the full diurnal cycle using radiation forcing and an interactive land surface model.
Based on these results, coherent turbulent structures in the convective boundary layer over non-flat terrain are studied in further detail. A conditional sampling method based on the concentration of a decaying passive tracer is implemented in order to identify the boundary-layer plumes objectively. Conditional sampling allows to quantify the contribution of plume structures to the vertical transport of heat and moisture. In case of the idealized valley, vertical transport by coherent structures is the dominant contribution to the turbulent components of both heat and moisture flux. It is comparable in magnitude to the advective transport by the mean slope-wind circulation, although it is more important for heat than for moisture transport. A set of less idealized simulations considers the flow over three-dimensional terrain. In this case, conditional sampling is carried out by using a simple domain-decomposition approach. We demonstrate that thermal updrafts are generally more frequent on hill tops than over the surroundings, but they are less persistent on the windward sides when large-scale winds are present in the free atmosphere.
The tools for flow decomposition and budget analysis are also applied in another idealized case with a quasi-two-dimensional valley featuring the stable boundary layer. Here, the formation of a low stratus cloud is investigated. The main driver for the cloud formation is radiative cooling due to outgoing longwave radiation. Despite a purely horizontal flow, the advection terms in the prognostic equations for heat and moisture produce vertical mixing across the upper cloud edge leading to a loss of cloud water content. However, this behavior is not due to any kind of thermally-driven circulation. Instead, this spurious mixing is caused by the diffusive error of the advection scheme in regions where the sloping surfaces of the terrain-following vertical coordinate intersect the cloud top. It is shown that the intensity of the (spurious) numerical diffusion strongly depends on the horizontal resolution, the order of advection, and the choice of the scalar advection scheme. A LES with 4 m horizontal resolution serves as a reference. For horizontal resolutions of a few hundred meters, carried out with a model setup as it is used in Numerical Weather Prediction, a strong reduction of the simulated liquid-water path is observed. In order to keep the (spurious) numerical diffusion at coarser resolutions small, at least a fifth-order advection scheme should be used. In the present case, a WENO scalar advection scheme turns out to increase the numerical diffusion along a sharp cloud edge compared to an upwind scheme. Furthermore, the choice of the vertical coordinate has a strong impact on the simulated liquid-water path over orography. With a modified definition of the terrain-following sigma coordinate, it is possible to produce cloud water where the classical sigma coordinate does not allow any cloud formation.
We present the prototype of a regional climate system model based on the COSMO-CLM regional climate model coupled with several model components, analyze the performance of the couplings and present a strategy to find an optimum configuration with respect to computational costs and time to solution.
The OASIS3-MCT coupler is used to couple COSMO-CLM with two land surface models (CLM and VEG3D), a regional ocean model for the Mediterranean Sea (NEMO-MED12), two ocean models for the North and Baltic Sea (NEMO-NORDIC and TRIMNP+CICE) and the atmospheric component of an earth system model (MPI-ESM). We present a unified OASIS3-MCT interface which handles all couplings in a similar way, minimizes the model source code modifications and describes the physics and numerics of the couplings. Furthermore, we discuss solutions for specific regional coupling problems like handling of different domains, multiple usage of MCT interpolation library and efficient exchange of 3D fields.
A series of real-case simulations over Europe has been conducted and the computational performance of the couplings has been analyzed. The usage of the LUCIA tool of the OASIS3-MCT coupler enabled separation of the direct costs of: coupling, load imbalance and additional computations. The resulting limits for time to solution and costs are shown and the potential of further improvement of the computational efficiency is summarized for each coupling.
It was found that the OASIS3-MCT coupler keeps the direct coupling costs of communication and horizontal interpolation small in comparison with the costs of the additional computations and load imbalance for all investigated couplings. For the first time this could be demonstrated for an exchange of approximately 450 2D fields per time step necessary for the atmosphere-atmosphere coupling between COSMO-CLM and MPI-ESM.
A procedure for finding an optimum configuration for each of the couplings was developed considering the time to solution and costs of the simulations. The optimum configurations are presented for sequential and concurrent coupling layouts. The procedure applied can be regarded as independent on the specific coupling layout and coupling details.
his study aims at a detailed characterization of an ultra-fine aerosol particle counting system for operation on board the Russian high altitude research aircraft M-55 "Geophysica" (maximum ceiling of 21 km). The COndensation PArticle counting Systems (COPAS) consists of an aerosol inlet and two dual-channel continuous flow Condensation Particle Counters (CPCs).
The aerosol inlet, adapted for COPAS measurements on board the M-55 "Geophysica", is described concerning aspiration, transmission, and transport losses. The counting efficiencies of the CPCs using the chlorofluorocarbon FC-43 as the working fluid are studied experimentally at two pressure conditions, 300 hPa and 70 hPa. Three COPAS channels are operated with different temperature differences between the saturator and the condenser block yielding smallest detectable particle sizes (dp50 – as 50% detection "cut off" diameters) of 6 nm, 11 nm, and 15 nm, respectively, at ambient pressure of 70 hPa. The fourth COPAS channel is operated with an aerosol heating line (250°C) for a determination of the non-volatile number of particles. The heating line is experimentally proven to volatilize pure H2SO4-H2O particles for a particle diameter (dp) range of 11 nm<dp<200 nm.
Additionally this study includes investigation to exclude auto-nucleation of the working fluid inside the CPCs. An instrumental inter-comparison (cross-correlation) has been performed for several measurement flights and mission flights in the Arctic and the Tropics are discussed. Finally, COPAS measurements are used for an aircraft plume crossing analysis.
A characterization of the ultra-fine aerosol particle counter COPAS (COndensation PArticle counting System) for operation on board the Russian high altitude research aircraft M-55 Geophysika is presented. The COPAS instrument consists of an aerosol inlet and two dual-channel continuous flow Condensation Particle Counters (CPCs) operated with the chlorofluorocarbon FC-43. It operates at pressures between 400 and 50 hPa for aerosol detection in the particle diameter (dp) range from 6 nm up to 1 micro m. The aerosol inlet, designed for the M-55, is characterized with respect to aspiration, transmission, and transport losses. The experimental characterization of counting efficiencies of three CPCs yields dp50 (50% detection particle diameter) of 6 nm, 11 nm, and 15 nm at temperature differences (DeltaT) between saturator and condenser of 17°C, 30°C, and 33°C, respectively. Non-volatile particles are quantified with a fourth CPC, with dp50=11 nm. It includes an aerosol heating line (250°C) to evaporate H2SO4-H2O particles of 11 nm<dp<200 nm at pressures between 70 and 300 hPa. An instrumental in-flight inter-comparison of the different COPAS CPCs yields correlation coefficients of 0.996 and 0.985. The particle emission index for the M-55 in the range of 1.4–8.4×10 16 kg -1 fuel burned has been estimated based on measurements of the Geophysika's own exhaust.
Das Wissen über die Wolkenmikrophysik und die Wechselwirkung zwischen Niederschlag und Aerosol ist ein wichtiger Baustein zur Optimierung von Klima- und Wettermodellen. Ein Großteil des Niederschlags in den mittleren Breiten fällt aus Mischphasenwolken, die aus unterkühlten Tröpfchen und Eispartikeln bestehen. Die Eispartikel bilden sich an speziellen Aerosolpartikeln, die als Eiskeime (INP) wirken können. Die Wahrscheinlichkeit eines Aerosols als Eiskeim zu wirken, nimmt mit abnehmender Temperatur und steigender Wassersättigung zu. Mineralstaubpartikel sind die häufigsten Eiskeime, die ab Temperaturen ≤−15°C aktiv sind, biologische Partikel wirken schon bei wärmeren Bedingungen. Große Wissenslücken bestehen noch bei der globalen Konzentration von Eiskeimen, inklusive deren geographischer und jahreszeitlicher Variabilität.
Im Zentrum der Experimente, die für diese Arbeit durchgeführt wurden, steht der Eiskeimzähler FRIDGE (Frankfurt Ice Deposition Freezing Experiment). Je nach Aufbau und Anwendung des Instruments werden zwei verschiedene Ansätze zur Aktivierung von Eiskeimen verfolgt. Die ursprüngliche und namensgebende Methode in Form einer Vakuum-Diffusionskammer wurde zur Untersuchung von Eisnukleation via Depositionsgefrieren (an INP_D) entwickelt (Klein et al., 2010). Danielczok (2015) nutzte einige Bestandteile des Analysegeräts, um auch Immersionsgefrieren (an INP_I) in Form von Tröpfchengefrieren à la Vali (1971) zu studieren. In der vorliegenden Arbeit wurde diese Anwendungsmöglichkeit von FRIDGE weiterentwickelt. Ein zentraler Schritt war dabei die präzise Charakterisierung des Gefrierverhaltens von Tröpfchen aus Reinstwasser ohne zusätzliches Aerosol. Die Einbeziehung dieses sogenannten Hintergrundgefrierens, das für jedes Instrument und Messverfahren spezifisch ist, ermöglichte es, die Minimaltemperatur, für die zuverlässige Ergebnisse produziert werden können, von −22°C auf −29°C herabzusetzen. Der dadurch hinzugewonnene Temperaturbereich ist für Eisnukleation in Mischphasenwolken äußerst relevant.
Beide Anwendungsmethoden wurden im Rahmen des Fifth International Workshop on Ice Nucleation – Phase 2 (FIN-02) sowie bei einer weiteren Kampagne zur Messung von Eisnukleation an Cellulosepartikeln mit über zwanzig anderen Eiskeimzählern verglichen. Mit FRIDGE als Diffusionskammer wurde für die Mehrheit der untersuchten Aerosoltypen eine zufriedenstellende Übereinstimmung mit den anderen Instrumenten beobachtet. Die Experimente mit gefrierenden Tröpfchen in FRIDGE erzielten ausnahmslos Ergebnisse, die inmitten der Werte der anderen Instrumente lagen. Die erfolgreiche Validierung – besonders der neuen Anwendungsmethode – war das erste Ziel dieser Arbeit und die notwendige Voraussetzung für die anschließenden Feldmessungen.
Atmosphärische Eiskeimkonzentrationen wurden in mehrwöchigen Feldmesskampagnen an drei sehr unterschiedlichen Orten und atmosphärischen Bedingungen untersucht: an der Hochalpinen Forschungsstation Jungfraujoch (JFJ), am Storm Peak Laboratory (SPL) in den Rocky Mountains und am Cyprus Atmospheric Observatory (CAO) in Zypern. Am JFJ wurde eine INP-Konzentration beobachtet, die um den Faktor 20 niedriger als an den anderen beiden Stationen war. Der Grund dafür war, dass sich das Jungfraujoch die meiste Zeit der Messungen in der freien Troposphäre befand. Dementsprechend waren die Bedingungen an der Station von aerosolpartikelarmer Luft mit wenigen Eiskeimen geprägt. An zwei Standorten wurde Mineralstaub als ein Parameter, der die lokale INP-Konzentration positiv beeinflusst, identifiziert. Sowohl am JFJ als auch am CAO erhöhte ferntransportierter Saharastaub die INP-Konzentration.
Die Kombination der zwei Analysemethoden, die Aerosolproben aus derselben Luft entweder in trockenem Ausgangszustand oder in Tröpfchen suspendiert untersuchen, offenbarte eine interessante Eigenschaft der INP. Es herrschte eine offensichtliche Parallelität von INP_D- und INP_I- Konzentrationen. Bei fast allen Messungen waren INP_I etwa 10-mal häufiger als INP_D. Die Aussage trifft gleichermaßen auf sehr niedrige Konzentrationen am JFJ wie auch auf hohe Konzentrationen am SPL und CAO zu. Die einzige Ausnahme bilden Cellulosepartikel. Daraus lässt sich schließen, dass INP_D und INP_I dieselben Partikel sind, die je nach Aktivierungskonditionen Eisnukleation unterschiedlich effektiv hervorrufen.
Die Ergebnisse der Beobachtungen der meteorologischen Station zu Osnabrück in den Jahren 1899 und 1900 sind in Form von Tabellen und Diagrammen zusammengefasst. Bei den Ergebnissen handelt es sich um die Regenhöhe, die Temperatur, die relative Feuchtigkeit, der Dunstdruck, die Windrichtung und der Druck.
Die Ergebnisse der Beobachtungen der meteorologischen Station zu Osnabrück in den Jahren 1891 und 1892 sind in Form von Tabellen und Diagrammen zusammengefasst. Bei den Ergebnissen handelt es sich um die Regenhöhe, die Temperatur, die relative Feuchtigkeit, der Dunstdruck, die Windrichtung und der Druck.
New particle formation in the upper free troposphere is a major global source of cloud condensation nuclei (CCN)1,2,3,4. However, the precursor vapours that drive the process are not well understood. With experiments performed under upper tropospheric conditions in the CERN CLOUD chamber, we show that nitric acid, sulfuric acid and ammonia form particles synergistically, at rates that are orders of magnitude faster than those from any two of the three components. The importance of this mechanism depends on the availability of ammonia, which was previously thought to be efficiently scavenged by cloud droplets during convection. However, surprisingly high concentrations of ammonia and ammonium nitrate have recently been observed in the upper troposphere over the Asian monsoon region5,6. Once particles have formed, co-condensation of ammonia and abundant nitric acid alone is sufficient to drive rapid growth to CCN sizes with only trace sulfate. Moreover, our measurements show that these CCN are also highly efficient ice nucleating particles—comparable to desert dust. Our model simulations confirm that ammonia is efficiently convected aloft during the Asian monsoon, driving rapid, multi-acid HNO3–H2SO4–NH3 nucleation in the upper troposphere and producing ice nucleating particles that spread across the mid-latitude Northern Hemisphere.
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.
Measurement of iodine species and sulfuric acid using bromide chemical ionization mass spectrometers
(2021)
Iodine species are important in the marine atmosphere for oxidation and new-particle formation. Understanding iodine chemistry and iodine new-particle formation requires high time resolution, high sensitivity, and simultaneous measurements of many iodine species. Here, we describe the application of a bromide chemical ionization mass spectrometer (Br-CIMS) to this task. During the iodine oxidation experiments in the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber, we have measured gas-phase iodine species and sulfuric acid using two Br-CIMS, one coupled to a Multi-scheme chemical IONization inlet (Br-MION-CIMS) and the other to a Filter Inlet for Gasses and AEROsols inlet (Br-FIGAERO-CIMS). From offline calibrations and intercomparisons with other instruments, we have quantified the sensitivities of the Br-MION-CIMS to HOI, I2, and H2SO4 and obtained detection limits of 5.8 × 106, 3.8 × 105, and 2.0 × 105 molec. cm−3, respectively, for a 2 min integration time. From binding energy calculations, we estimate the detection limit for HIO3 to be 1.2 × 105 molec. cm−3, based on an assumption of maximum sensitivity. Detection limits in the Br-FIGAERO-CIMS are around 1 order of magnitude higher than those in the Br-MION-CIMS; for example, the detection limits for HOI and HIO3 are 3.3 × 107 and 5.1 × 106 molec. cm−3, respectively. Our comparisons of the performance of the MION inlet and the FIGAERO inlet show that bromide chemical ionization mass spectrometers using either atmospheric pressure or reduced pressure interfaces are well-matched to measuring iodine species and sulfuric acid in marine environments.
Analyzing the impact of streamflow drought on hydroelectricity production: a global-scale study
(2021)
Electricity production by hydropower is negatively affected by drought. To understand and quantify risks of less than normal streamflow for hydroelectricity production (HP) at the global scale, we developed an HP model that simulates time series of monthly HP worldwide and thus enables analyzing the impact of drought on HP. The HP model is based on a new global hydropower database (GHD), containing 8,716 geo-localized plant records, and on monthly streamflow values computed by the global hydrological model WaterGAP with a spatial resolution of 0.5°. The GHD includes 44 attributes and covers 91.8% of the globally installed capacity. The HP model can reproduce HP trends, seasonality, and interannual variability that was caused by both (de)commissioning of hydropower plants and hydrological variability. It can also simulate streamflow drought and its impact on HP reasonably well. Global risk maps of HP reduction were generated for both 0.5° grid cells and countries, revealing that 67 out of the 134 countries with hydropower suffer, in 1 out of 10 years, from a reduction of more than 20% of mean annual HP and 18 countries from a reduction of more than 40%. The developed HP model enables advanced assessments of drought impacts on hydroelectricity at national to international levels.
In dieser Arbeit wird die Richtungsabhängigkeit seismischer Geschwindigkeiten im Erdmantel unterhalb Deutschlands und angrenzender Gebiete durch die Analyse der teleseismischen Kernphase SKS auf Doppelbrechung untersucht (Scherwellen-Splitting). Die Anisotropie wird durch die Splittingparameter Φ und δt beschrieben und erlaubt Rückschlüsse auf geodynamische Prozesse.
Untersucht werden Aufzeichnungen des Deutschen Seismologischen Regionalnetzes (GRSN) und assoziierter Stationen aus dem Zeitraum von 1993 bis 2009. Für drei Stationen des Gräfenberg-Arrays (GRF-Array) sind Wellenformen ab 1976 verfügbar, welche damit einen weltweit einmaligen Datensatz liefern.
Auf Grund des stetigen Ausbaus der seismologischen Netze und des langen Beobachtungszeitraumes können über 3.000 Seismogramme ausgewertet werden. Der Hauptteil dieser Arbeit besteht daher in der Entwicklung einer automatischen Methodik zur Analyse von SKS-Splitting: ADORE ("Automatische Bestimmung von DOppelbrechnungsparametern in REgionalseismischen Netzwerken"). Für regionale Netze wie das GRSN gewährleistet ADORE eine objektive Bestimmung der Splittingparameter. Zunächst wird das seismologische Netzwerk als seismisches Array aufgefasst, um durch eine Frequenz-Wellenzahl-Analyse den Einsatz der SKS-Phase ohne manuellen Eingriff zu bestimmen. Die Berechnung der Splittingparameter erfolgt durch eine Inversion nach der Methode der Minimierung des transversalen Energieanteils. Automatisch wird das optimale Fenster um den SKS-Einsatz positioniert, für jede Beben-Stations-Kombination werden dazu 3.600 Einzelinversionen durchgeführt.
Um diese Vielzahl von Auswertungen in akzeptabler Zeit zu berechnen, nutzt ADORE moderne Rechnerarchitekturen aus, verteilt die Berechnungen auf mehrere Computer im lokalen Netzwerk und erzielt damit eine Beschleunigung um einen Faktor 60.
Die Analyse des gesamten Datensatzes ergibt folgende Ergebnisse: An allen analysierten Stationen wurde ein Scherwellen-Splitting festgestellt, der Stationsuntergrund weist somit überall Anisotropie auf. Für 240 Erdbeben können insgesamt 494 Wertepaare mit höchster Qualität bestimmt werden.
Unter der Annahme einer homogenen ungeneigten anisotropen Schicht unterhalb der jeweiligen Station können die Einzelmessungen pro Station gemittelt werden. Damit sind Regionen mit ähnlichen Merkmalen gut zu identifizieren: Im Norden Deutschlands herrschen NW-SO-, in der Mitte W-O-Richtungen und im Süden SW-NO-Richtungen vor.
Die Verzögerungszeiten liegen im Bereich zwischen 1.0 (Station Taunus) und 2.2 Sekunden (Tannenbergsthal, TANN). Auf Grund des hohen Wertes sind die Ursachen für die hier beobachteten Zeiten dem Erdmantel und nicht der Kruste zuzuordnen. Die bevorzugte Ausrichtung von anisotropen Kristallen auf Grund von Fließprozessen von Mantelmaterial ist Quelle der beobachteten Anisotropie. Rezente Fließprozesse von Mantelmaterial sind vor allem an der Unterkante der Lithosphäre wahrscheinlich. Durch Gebirgsbildungsprozesse, vorhandene Gebirgswurzeln oder regionale Veränderungen in der Mächtigkeit der Lithosphäre entstehen Barrieren für viskoses Mantelmaterial.
Als tektonische Ursachen für die hier gemessenen Orientierungen ist im Norden die Tornquist-Teisseyre-Linie (TTZ), in der Mitte die Variszische Gebirgsbildung und im Süden Einflüsse des Alpenbogens anzusehen. Ausnahmen bilden die Stationen Clausthal-Zellerfeld (CLZ), Rügen und Black-Forest-Observatory (BFO). Während bei letzterer ein Einfluss der Spreizungszone des Oberrheingrabens zu vermuten ist, scheint die Intrusion des Brockengranits die Beobachtungen an CLZ zu prägen. Rügen liegt in einer Übergangszone zwischen Sorgenfrei-Tornquist-Zone und TTZ.
Durch die Vielzahl von vorhandenen Einzelmessungen lassen sich an manchen Stationen komplexe Modelle untersuchen. Dazu zählen neben Gradientmodellen auch die geneigte Schicht und Zwei-Schicht-Modelle. Für sechs Stationen kann ein Zwei-Schicht-Modell erstellt werden: BFO, Gräfenberg A1, Fürstenfeldbruck (FUR), Rüdersdorf (RUE), TANN und Unterbreitzbach (UBBA). Die Interpretation der Richtungen von oberer und unterer Schicht gelingt für einen Teil der genannten Stationen: An BFO liegt die Orientierung der unteren Schicht parallel zur Vorzugsrichtung der variszischen Gebirgsbildung, jene der obere Schicht antiparallel zur Spreizungsrichtung des Rheingrabens. Für die Station FUR ist eine Überlagerung mit der Streichrichtung des Alpenmassivs zu beobachten. An GRA1 wird die untere Schicht offenbar durch rezente oder eingefrorene Anisotropie des Böhmischen Massivs bzw. des Eger-Riftsystems beeinflusst. Eine vergleichbare Wirkung ist durch die TTZ an der Station RUE zu erkennen.
ADORE wurde weiterhin auf einen Datensatz des temporären RIFTLINK-Projektes angewandt.
The oxidation state of sulfur in slab fluids is controversial, with both dominantly oxidized and reduced species proposed. Here we use in situ X-ray absorption spectroscopy analysis of sulfur-in-apatite to monitor changes in the oxidation state of sulfur during high-P metasomatism by slab fluids in the subduction channel. Our samples include a 73 cm continuous transect of reaction zones between a metagabbroic eclogite block and serpentinite matrix from a mélange zone on the island of Syros, Greece. The block core consists of garnet, omphacite, phengite, paragonite, epidote-clinozoisite, and rutile. In this region, apatite is only observed as elongate inclusions in omphacite cores. From the core outwards micas are increasingly replaced by epidote-clinozoisite, garnets are smaller and more frequent, pyrite + bornite is observed as inclusions in recrystallized omphacite, and apatite is increasingly abundant in the matrix and inclusions in garnet. A major transition at 48 cm separates an assemblage of Ca-Na amphibole, omphacite, chlorite, pyrite, and apatite from the inner garnet-bearing eclogite assemblages. Omphacite disappears from the assemblage at ~56 cm and amphibole compositions sharply transition to tremolite at 59 cm. Finally, the assemblage tremolite + talc + pyrite is observed after ~70 cm.Apatites in the eclogite assemblages exclusively display S6+ peaks in their absorption spectra. This includes apatite inclusions in omphacite in the least altered lithology, as well as matrix apatite and isolated apatite inclusions in garnet in the outermost metasomatized eclogite zone. In the intermediate pyrite-rich (~1-5 vol %) amphibole + omphacite + chlorite zone, apatite displays a strong S1- absorption peak in most grains, with rare analyses showing mixed S1- and S6+. Finally, apatite in the outermost tremolite-bearing assemblages only displays a S6+ peak. The pyrite-rich zone at 48 cm occurs at the initial interface between the serpentinite matrix and eclogite block, characterized by a dramatic decrease in Na content and Mg#. Our data suggest that reduction of S6+ in infiltrating fluids to S1- in pyrite became focused as Fe diffused across the steep Mg# gradient, resulting in pyrite precipitation. In contrast, S reduction in the Mg-rich tremolite-dominant portions of the transect was limited by a lack of Fe, resulting in low modes of pyrite and fluid buffered S6+ in apatite. Finally, S6+-bearing apatite is also observed in reaction zone lithologies from elsewhere on Syros, suggesting our observations are not isolated.Two important conclusions are drawn from these data and observations: (1) In the case of Syros, slab fluids at eclogite-facies conditions carried oxidized S6+, and (2) The interaction of these fluids with eclogites composed of ferrous-Fe silicates resulted in extensive sulfide precipitation.
Sulfur in the slab: a sulfur-isotopes and thermodynamic-modeling perspective from exhumed terranes
(2022)
Sulfur is a key element in the subduction zone-volcanic arc system; however, the mechanism(s) that recycle sulfur from the slab into the overlying volcanic arc are debated. Here we summarize recent advances in quantifying this component of the deep sulfur cycle. First, primary metamorphic or inherited sulfides in oceanic-type eclogites are only rarely observed as inclusions and are typically absent from the rock matrix. Additionally, sulfides are relatively common in rocks metasomatized at the slab-mantle interface by slab-derived fluids during exhumation. Combined, these two observations suggest that sulfur loss from subducted mafic crust is relatively efficient. Thermodynamic modeling in Perple_X using the Holland and Powell (2011) database combined with the Deep Earth Water model suggests that the efficiency and speciation of sulfur loss varies depending on the degree of seafloor alteration prior to subduction and the geothermal gradient of the slab. In relatively cold subduction zones, such as Honshu, slab-fluids derived from subducted mafic crust are predicted to exhibit elevated concentrations of HSO4-, SO42-, HSO3-, and CaSO4(aq), whereas hot subduction zones, such as Cascadia, are predicted to produce slab fluids enriched in HS- and H2S at lower pressures. The oxidation of sulfur expelled from subducted pyrite is balanced by the reduction of Fe3+ to Fe2+, consistent with the low Fe3+/SFe of exhumed eclogites relative to blueschists and altered oceanic crust. Where oxidized S-bearing fluids are produced, they are anticipated to interact with more reduced rocks at the slab-mantle interface and within the mantle wedge, resulting in sulfide precipitation and significant isotopic fractionation. The δ34S values of slab fluids are estimated to fall between -11 and +8 ‰. Rayleigh fractionation during progressive fluid-rock interaction results in fractionations of tens of per mil as oxidized species are depleted and sulfides are precipitated, resulting in δ34S values of sulfides that easily span the -21.7 to +13.9 ‰ range observed in metasomatic sulfides in exhumed high-pressure rocks. However, in subduction zones where reduced species prevail, the S isotopic signature of slab fluids is expected to reflect their source and will exhibit a narrower range in δ34S values. As a result, the δ34S values measured in arc magmas may not always be a reliable indicator of the contribution of different components of the slab, such as sediments vs. AOC. Additionally, the impact of S recycling on the oxygen fugacity of arc magmas is expected to vary both spatially and temporally throughout Earth history.
Titanite is a potentially powerful U–Pb petrochronometer that may record metamorphism, metasomatism, and deformation. Titanite may also incorporate significant inherited Pb, which may lead to inaccurate and geologically ambiguous U–Pb dates if a proper correction is not or cannot be applied. Here, we present laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS)-derived titanite U–Pb dates and trace element concentrations for two banded calcsilicate gneisses from south-central Maine, USA (SSP18-1A and SSP18-1B). Single spot common Pb-corrected dates range from 400 to 280 Ma with ±12–20 Ma propagated 2SE. Titanite grains in sample SSP18-1B exhibit regular core-to-rim variations in texture, composition, and date. We identify four titanite populations: (1) 397 ± 5 Ma (95% CL) low Y + HREE cores and mottled grains, (2) 370 ± 7 Ma high Y + REE mantles and cores, (3) 342 ± 6 Ma cores with high Y + REE and no Eu anomaly, and (4) 295 ± 6 Ma LREE-depleted rims. We interpret the increase in titanite Y + HREE between ca. 397 and ca. 370 Ma to constrain the timing of diopside fracturing and recrystallization and amphibole breakdown. Apparent Zr-in-titanite temperatures (803 ± 36°C at 0.5 ± 0.2 GPa) and increased XDi suggest a thermal maximum at ca. 370 Ma. Population 3 domains dated to ca. 342 Ma exhibit no Eu anomaly and are observed only in compositional bands dominated by diopside (>80 vol%), suggesting limited equilibrium between titanite and plagioclase. Finally, low LREE and high U/Th in Population 4 titanite dates the formation of hydrous phases, such as allanite, during high XH2O fluid infiltration at ca. 295 Ma. In contrast to the well-defined date–composition–texture relationships observed for titanite from SSP18-1B, titanite grains from sample SSP18-1A exhibit complex zoning patterns and little correlation between texture, composition, and date. We hypothesize that the incorporation of variable amounts of radiogenic Pb from dissolved titanite into recrystallized domains resulted in mixed dates spanning 380–330 Ma. Although titanite may reliably record multiple phases of metamorphism, these data highlight the importance of considering U–Pb data along with chemical and textural data to screen for inherited radiogenic Pb.
The climate system can be regarded as a dynamic nonlinear system. Thus, traditional linear statistical methods fail to model the nonlinearities of such a system. These nonlinearities render it necessary to find alternative statistical techniques. Since artificial neural network models (NNM) represent such a nonlinear statistical method their use in analyzing the climate system has been studied for a couple of years now. Most authors use the standard Backpropagation Network (BPN) for their investigations, although this specific model architecture carries a certain risk of over-/underfitting. Here we use the so called Cauchy Machine (CM) with an implemented Fast Simulated Annealing schedule (FSA) (Szu, 1986) for the purpose of attributing and detecting anthropogenic climate change instead. Under certain conditions the CM-FSA guarantees to find the global minimum of a yet undefined cost function (Geman and Geman, 1986). In addition to potential anthropogenic influences on climate (greenhouse gases (GHG), sulphur dioxide (SO2)) natural influences on near surface air temperature (variations of solar activity, explosive volcanism and the El Nino = Southern Oscillation phenomenon) serve as model inputs. The simulations are carried out on different spatial scales: global and area weighted averages. In addition, a multiple linear regression analysis serves as a linear reference. It is shown that the adaptive nonlinear CM-FSA algorithm captures the dynamics of the climate system to a great extent. However, free parameters of this specific network architecture have to be optimized subjectively. The quality of the simulations obtained by the CM-FSA algorithm exceeds the results of a multiple linear regression model; the simulation quality on the global scale amounts up to 81% explained variance. Furthermore the combined anthropogenic effect corresponds to the observed increase in temperature Jones et al. (1994), updated by Jones (1999a), for the examined period 1856–1998 on all investigated scales. In accordance to recent findings of physical climate models, the CM-FSA succeeds with the detection of anthropogenic induced climate change on a high significance level. Thus, the CMFSA algorithm can be regarded as a suitable nonlinear statistical tool for modeling and diagnosing the climate system.
Attribution and detection of anthropogenic climate change using a backpropagation neural network
(2002)
The climate system can be regarded as a dynamic nonlinear system. Thus traditional linear statistical methods are not suited to describe the nonlinearities of this system which renders it necessary to find alternative statistical techniques to model those nonlinear properties. In addition to an earlier paper on this subject (WALTER et al., 1998), the problem of attribution and detection of the observed climate change is addressed here using a nonlinear Backpropagation Neural Network (BPN). In addition to potential anthropogenic influences on climate (CO2-equivalent concentrations, called greenhouse gases, GHG and SO2 emissions) natural influences on surface air temperature (variations of solar activity, volcanism and the El Niño/Southern Oscillation phenomenon) are integrated into the simulations as well. It is shown that the adaptive BPN algorithm captures the dynamics of the climate system, i.e. global and area weighted mean temperature anomalies, to a great extent. However, free parameters of this network architecture have to be optimized in a time consuming trial-and-error process. The simulation quality obtained by the BPN exceeds the results of those from a linear model by far; the simulation quality on the global scale amounts to 84% explained variance. Additionally the results of the nonlinear algorithm are plausible in a physical sense, i.e. amplitude and time structure. Nevertheless they cover a broad range, e.g. the GHG-signal on the global scale ranges from 0.37 K to 1.65 K warming for the time period 1856-1998. However the simulated amplitudes are situated within the discussed range (HOUGHTON et al., 2001). Additionally the combined anthropogenic effect corresponds to the observed increase in temperature for the examined time period. In addition to that, the BPN succeeds with the detection of anthropogenic induced climate change on a high significance level. Therefore the concept of neural networks can be regarded as a suitable nonlinear statistical tool for modeling and diagnosing the climate system.
Simulation of global temperature variations and signal detection studies using neural networks
(1998)
The concept of neural network models (NNM) is a statistical strategy which can be used if a superposition of any forcing mechanisms leads to any effects and if a sufficient related observational data base is available. In comparison to multiple regression analysis (MRA), the main advantages are that NNM is an appropriate tool also in the case of non-linear cause-effect relations and that interactions of the forcing mechanisms are allowed. In comparison to more sophisticated methods like general circulation models (GCM), the main advantage is that details of the physical background like feedbacks can be unknown. Neural networks learn from observations which reflect feedbacks implicitly. The disadvantage, of course, is that the physical background is neglected. In addition, the results prove to be sensitively dependent from the network architecture like the number of hidden neurons or the initialisation of learning parameters. We used a supervised backpropagation network (BPN) with three neuron layers, an unsupervised Kohonen network (KHN) and a combination of both called counterpropagation network (CPN). These concepts are tested in respect to their ability to simulate the observed global as well as hemispheric mean surface air temperature annual variations 1874 - 1993 if parameter time series of the following forcing mechanisms are incorporated : equivalent CO2 concentrations, tropospheric sulfate aerosol concentrations (both anthropogenic), volcanism, solar activity, and ENSO (all natural). It arises that in this way up to 83% of the observed temperature variance can be explained, significantly more than by MRA. The implication of the North Atlantic Oscillation does not improve these results. On a global average, the greenhouse gas (GHG) signal so far is assessed to be 0.9 - 1.3 K (warming), the sulfate signal 0.2 - 0.4 K (cooling), results which are in close similarity to the GCM findings published in the recent IPCC Report. The related signals of the natural forcing mechanisms considered cover amplitudes of 0.1 - 0.3 K. Our best NNM estimate of the GHG doubling signal amounts to 2.1K, equilibrium, or 1.7 K, transient, respectively.
Increasing atmospheric CO2 stimulates photosynthesis which can increase net primary production (NPP), but at longer timescales may not necessarily increase plant biomass. Here we analyse the four decade-long CO2-enrichment experiments in woody ecosystems that measured total NPP and biomass. CO2 enrichment increased biomass increment by 1.05 ± 0.26 kg C m−2 over a full decade, a 29.1 ± 11.7% stimulation of biomass gain in these early-secondary-succession temperate ecosystems. This response is predictable by combining the CO2 response of NPP (0.16 ± 0.03 kg C m−2 y−1) and the CO2-independent, linear slope between biomass increment and cumulative NPP (0.55 ± 0.17). An ensemble of terrestrial ecosystem models fail to predict both terms correctly. Allocation to wood was a driver of across-site, and across-model, response variability and together with CO2-independence of biomass retention highlights the value of understanding drivers of wood allocation under ambient conditions to correctly interpret and predict CO2 responses.
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.
Following votes in the Coniacian Working Group, the Cretaceous Subcommission and the International Commission on Stratigraphy, on May 1st, 2021, the International Union of Geological Sciences voted unanimously to ratify the Global Stratotype Section and Point (GSSP) proposal for the base of the Coniacian Stage of the Upper Cretaceous Series and Cretaceous System. The lower boundary of the Coniacian Stage is placed at the base of Bed 46 of the Salzgitter-Salder section in northern Germany. The boundary is defined by the first appearance of the inoceramid bivalve species Cremnoceramus deformis erectus (Meek) and complemented by the Navigation carbon isotope event. Additional data include the bivalve genus Didymotis, foraminifera, ammonite, nannofossil and organic-walled dinoflagellate cyst events. Three auxiliary sections (Słupia Nadbrzeżna, central Poland; Střeleč, Czech Republic; El Rosario, NE Mexico) supplement the details of the boundary record in various facies, and in differing geographic and biogeographic contexts.
The formation of secondary particles in the atmosphere accounts for more than half of global cloud condensation nuclei. Experiments at the CERN CLOUD (Cosmics Leaving OUtdoor Droplets) chamber have underlined the importance of ions for new particle formation, but quantifying their effect in the atmosphere remains challenging. By using a novel instrument setup consisting of two nano-particle counters, one of them equipped with an ion filter, we were able to further investigate the ion-related mechanisms of new particle formation. In autumn 2015, we carried out experiments at CLOUD on four systems of different chemical compositions involving monoterpenes, sulfuric acid, nitrogen oxides, and ammonia. We measured the influence of ions on the nucleation rates under precisely controlled and atmospherically relevant conditions. Our results indicate that ions enhance the nucleation process when the charge is necessary to stabilize newly formed clusters, i.e. in conditions where neutral clusters are unstable. For charged clusters that were formed by ion-induced nucleation, we were able to measure, for the first time, their progressive neutralization due to recombination with oppositely charged ions. A large fraction of the clusters carried a charge at 1.2 nm diameter. However, depending on particle growth rates and ion concentrations, charged clusters were largely neutralized by ion–ion recombination before they grew to 2.2 nm. At this size, more than 90 % of particles were neutral. In other words, particles may originate from ion-induced nucleation, although they are neutral upon detection at diameters larger than 2.2 nm. Observations at Hyytiälä, Finland, showed lower ion concentrations and a lower contribution of ion-induced nucleation than measured at CLOUD under similar conditions. Although this can be partly explained by the observation that ion-induced fractions decrease towards lower ion concentrations, further investigations are needed to resolve the origin of the discrepancy.
A new method for size-resolved chemical analysis of nucleation mode aerosol particles (size range from ∼10 to ∼30 nm) is presented. The Thermal Desorption Differential Mobility Analyzer (TD-DMA) uses an online, discontinuous principle. The particles are charged, a specific size is selected by differential mobility analysis and they are collected on a filament by electrostatic precipitation. Subsequently, the sampled mass is evaporated in a clean carrier gas and analyzed by a chemical ionization mass spectrometer. Gas-phase measurements are performed with the same mass spectrometer during the sampling of particles. The characterization shows reproducible results, with a particle size resolution of 1.19 and the transmission efficiency for 15 nm particles being slightly above 50 %. The signal from the evaporation of a test substance can be detected starting from 0.01 ng and shows a linear response in the mass spectrometer. Instrument operation in the range of pg m−3 is demonstrated by an example measurement of 15 nm particles produced by nucleation from dimethylamine, sulfuric acid and water.
A new method for size resolved chemical analysis of nucleation mode aerosol particles (size range from ~10 to ~30 nm) is presented. The Thermal Desorption Differential Mobility Analyzer (TD-DMA) uses an online, discontinuous principle. The particles are charged, a specific size is selected by differential mobility analysis and they are collected on a filament by electrostatic precipitation. Subsequently, the sampled mass is evaporated in a clean carrier gas and analyzed by a chemical ionization mass spectrometer. Gas phase measurements are performed with the same mass spectrometer during the sampling of particles. The characterization shows reproducible results, with a particle size resolution of 1.19 and the transmission efficiency for 15 nm particles being slightly above 50 %. The signal from the evaporation of a test substance can be detected starting from 0.01 ng and shows a linear response in the mass spectrometer. Instrument operation in the range of pg/m3 is demonstrated by an example measurement of 15 nm particles produced by nucleation from dimethylamine, sulfuric acid and water.
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.
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.
AirCore samplers have been increasingly used to capture vertical profiles of trace gases reaching from the ground up to about 30 km, in order to validate remote sens- ing instruments and to investigate transport processes in the stratosphere. When deployed to a weather balloon, accu- rately attributing the trace gas measurements to the sampling altitudes is nontrivial, especially in the stratosphere. In this paper we present the CO-spiking experiment, which can be deployed to any AirCore on any platform in order to evalu- ate different computational altitude attribution processes and to experimentally derive the vertical resolution of the profile by injecting small volumes of signal gas at predefined GPS altitudes during sampling. We performed two CO-spiking flights with an AirCore from the Goethe University Frankfurt (GUF) deployed to a weather balloon in Traînou, France, in June 2019. The altitude retrieval based on an instantaneous pressure equilibrium assumption slightly overestimates the sampling altitudes, especially at the top of the profiles. For these two flights our altitude attribution is accurate within 250 m below 20 km. Above 20 km the positive bias becomes larger and reaches up to 1.2 km at 27 km altitude. Differences in descent velocities are shown to have a major impact on the altitude attribution bias. We parameterize the time lag between the theoretically attributed altitude and the actual CO-spike release altitude for both flights together and use it to empirically correct our AirCore altitude retrieval. Regard- ing the corrected profiles, the altitude attribution is accurate within ±120 m throughout the profile. Further investigations are needed in order to test for the scope of validity of this correction parameter regarding different ambient conditions and maximum flight altitudes. We derive the vertical resolu- tion from the CO spikes of both flights and compare it to the modeled vertical resolution. The modeled vertical resolution is too optimistic compared to the experimentally derived res- olution throughout the profile, albeit agreeing within 220 m. All our findings derived from the two CO-spiking flights are strictly bound to the GUF AirCore dimensions. The newly introduced CO-spiking experiment can be used to test differ- ent combinations of AirCore configurations and platforms in future studies.
Over recent decades, the global population has been rapidly increasing and human activities have altered terrestrial water fluxes to an unprecedented extent. The phenomenal growth of the human footprint has significantly modified hydrological processes in various ways (e.g. irrigation, artificial dams, and water diversion) and at various scales (from a watershed to the globe). During the early 1990s, awareness of the potential for increased water scarcity led to the first detailed global water resource assessments. Shortly thereafter, in order to analyse the human perturbation on terrestrial water resources, the first generation of large-scale hydrological models (LHMs) was produced. However, at this early stage few models considered the interaction between terrestrial water fluxes and human activities, including water use and reservoir regulation, and even fewer models distinguished water use from surface water and groundwater resources. Since the early 2000s, a growing number of LHMs have incorporated human impacts on the hydrological cycle, yet the representation of human activities in hydrological models remains challenging. In this paper we provide a synthesis of progress in the development and application of human impact modelling in LHMs. We highlight a number of key challenges and discuss possible improvements in order to better represent the human–water interface in hydrological models.
During this study clumped isotope analysis of carbonates was established at the Goethe University of Frankfurt, Germany. Therefore, preparation protocols and analytical parameters were elaborated to obtain precise and accurate Δ47 data. Briefly, analyte CO2 was cleaned cryogenically using glass extraction lines to remove traces of water that enable re-equilibration of C–O bonds in the gases. Furthermore, analyte CO2 was passed through a gas chromatograph (GC) to clean it from contaminants that produce isobaric interferences with m/z 47. Initially, phosphoric acid digestions of carbonates was conducted at 25 °C in McCrea-type reaction vessels. Afterwards samples were reacted at 90 °C using a common acid bath. Mass spectrometric analyses were performed using a MAT 253 equipped with a dual inlet system. Δ47 values were directly projected to the absolute scale using CO2 gases equilibrated at distinct temperatures.
In cooperation with Stefano Bernasconi and his research group at ETH Zurich we studied the non-linearity that occurs for the measurement of m/z 47. This effect results from secondary electrons created by the m/z 44 beam. These electrons cause a negative background on the m/z 47 collector. A correction procedure was proposed that relies on the determination of the negative background on the m/z 47 Faraday cup. This approach might reduce time-consuming analyses of heated gases which were used so far to account for the observed non-linearity. However, the suggested correction of the negative background on the m/z 47 cup is only applicable if the slit width of the m/z 44 beam is significantly wider than that of the m/z 47 beam.
This thesis, furthermore, presents a comparison of the different phosphoric acid digestion techniques which are commonly used for carbonate clumped isotope analysis. For calcitic and aragonitic material digested at 25 °C in McCrea-type vessels we observed that the sample size has an effect on Δ47 data: higher mean Δ47 values and a larger scatter of data were received for samples <7 mg than for larger aliquots. For carbonate samples digested at 90 °C in a common acid bath no sample size effect was determined. We assume that secondary re-equilibration of CO2 with water preferentially occurs at 25 °C producing the observed differences. However, a sample size effect can be avoided if reaction temperature is increased to 90 °C.
In order to make carbonate Δ47 data obtained from acid digestions at 90 °C comparable to Δ47 data received from reactions at 25 °C the difference of the acid fractionation factores (Δ47*25-90) between both temperatures has to be known. For the determination of the Δ47*25-90 value we have considered Δ47 data made at 25 °C from samples >7 mg only. For calicte and aragonite we obtained differences in fractionation factores of 0.075‰ and 0.066‰, respectively. These Δ47*25-90 values are coincident with the theoretical prediction of 0.069‰ proposed for calcite (Guo et al., 2009).
Moreover, this dissertation comprises a calibration study of the clumped isotope thermometer based on various natural calcites that grew between 9 and 38 °C. The samples include a brachiopod shell, a bivalve shell, an eggshell of an ostrich and foraminifera tests which formed from distinct biomineralizing processes. Furthermore we included an authigenic carbonate crystallized from biological-induced precipitation. The following linear relationship between 1/T2 and Δ47 was determined (with Δ47 in ‰ and T in K):
Δ47 = 0.0327 (± 0.0026) x 106 / T2 + 0.3030 (± 0.0308) (R2 = 0.9915)
This equation differs from the pioneering Ghosh et al. (2006a) calibration. However, our regression line is statistically indistinguishable from that of Henkes et al. (2013) which is based on aragonitic mollusks and calcitic brachiopod shells. Both studies have in common that calibration data were, at first, directly referenced to the absolute scale. In addition, both datasets rely on similar digestion techniques. Furthermore, the two calibrations are conform with the theoretical prediction of Guo et al. (2009).
The calcite calibration of the clumped isotope paleothermometer received in this study was applied to Δ47 data measured for Silurian brachiopods shells from Gotland/Sweden. Prior to isotopic analysis the fossils were intensively investigated for their preservation state (CL, SEM, trace elements). The lowest T(Δ47) values of ca. 28 to 33 °C were estimated from ultrastructurally well-preserved regions of some shells. For these samples also the lowest δ18Ow values of Silurian seawater were determined. These estimates of ca. −1‰ confirm the assumption that the δ18O value of the Silurian ocean was buffered to (0 ± 1)‰.
Nevertheless, most studied shells were characterized by a patchwork of pristine and altered shell portions resulting in elevated T(Δ47) values which plot mostly between 40 and 60 °C. Our results indicate that the clumped isotopic composition of the shells were altered at low water-rock ratios, not affecting the δ18O values. Δ47 and δ18O data of associated diagenetic phases (sparitic and micritic phases of the inner fillings of the fossils) provide evidence that the sparitic cements grew during several diagenetic events which occurred at different temperatures in fluid-buffered systems. We, furthermore, conclude that the micritic phases lithified at a very early diagenetic stage with the δ18O values being most probably close to a Silurian seawater composition
Der am Südrande des Harzes existierende etwa 100 km lange Ausstrich von Zechsteinschichten bietet mit seinen Gipsen, Anhydriten und Dolomiten gute Voraussetzungen zur Entstehung einer Karstlandschaft. Er erstreckt sich von Badenhausen im Landkreis Osterode über den Landkreis Nordhausen bis hin nach Pölsfeld im Landkreis Sangerhausen.
Motivated by the question of whether and how wave–wave interactions should be implemented into atmospheric gravity-wave parametrizations, the modulation of triadic gravity-wave interactions by a slowly varying and vertically sheared mean flow is considered for a non-rotating Boussinesq fluid with constant stratification. An analysis using a multiple-scale WKBJ (Wentzel–Kramers–Brillouin–Jeffreys) expansion identifies two distinct scaling regimes, a linear off-resonance regime, and a nonlinear near-resonance regime. Simplifying the near-resonance interaction equations allows for the construction of a parametrization for the triadic energy exchange which has been implemented into a one-dimensional WKBJ ray-tracing code. Theory and numerical implementation are validated for test cases where two wave trains generate a third wave train while spectrally passing through resonance. In various settings, of interacting vertical wavenumbers, mean-flow shear, and initial wave amplitudes, the WKBJ simulations are generally in good agreement with wave-resolving simulations. Both stronger mean-flow shear and smaller wave amplitudes suppress the energy exchange among a resonantly interacting triad. Experiments with mean-flow shear as strong as in the vicinity of atmospheric jets suggest that internal gravity-wave dynamics are dominated in such regions by wave modulation. However, triadic gravity-wave interactions are likely to be relevant in weakly sheared regions of the atmosphere.
This thesis deals with the analysis of “presolar” silicates and oxides by high resolution mass spectrometry and electron microscopy techniques. This “stardust” was identified by its extreme oxygen isotopic anomalies, which point to nucleosynthetic reactions in stellar interiors, in the carbonaceous chondrite Acfer 094. Isotopic, chemical and mineralogical studies on these stardust grains therefore allow the testing of astrophysical questions on Earth, which are otherwise only accessible by spectroscopy and theoretical models. The class of presolar silicates has been identified only six years ago in 2002, although it was known already from spectroscopic observations that silicates represent the most abundant type of dust in the galaxy. The development of the “NanoSIMS” was a crucial step in this respect, because this ion probe with its superior spatial resolution of only 50 nm allowed the detection of the typically 300 nm sized presolar silicates. A total of 142 presolar silicates and 20 presolar oxides were identified within Acfer 094, whose matrix therefore contains 163 ± 14 ppm presolar silicates and 26 ± 6 ppm presolar oxides. This is among the highest amounts reported so far for any primitive solar system material. The majority of detected stardust grains derive from asymptotic giant branch stars of 1 – 2.5 Msun and close-to-solar or slightly lower-than-solar metallicity. However, by measuring the Si isotopic compositions of some enigmatic grains, it could be shown that there is a sub-class of presolar silicates characterized by an extreme enrichment of 17O and a moderate enhancement of 30Si relative to solar, whose origins might be explained by formation in binary stellar systems. About 10% of all grains exhibit an enrichment in 18O and some of them also of 28Si relative to solar, which most likely point to an origin in type II supernova explosions. The Si isotopic measurements also allowed to quantify the effect of the s-process on the Si isotopes in low-mass asymptotic giant branch stars. The results agree well with theoretical predictions. The grains were furthermore characterized by SEM and the chemistries of about half of the grains were determined by Auger electron spectroscopy. The majority of grain morphologies are consistent with what is expected from condensation experiments. However, a lot of grains are altered by Fe-rich minerals, which are either of primary condensation or of secondary ISM or solar nebula origin. Furthermore, complex presolar grains consisting of refractory Al-rich grains attached to silicate material could be identified, which have been predicted by condensation theory and observational evidence. Nine presolar silicates were analyzed by combined NanoSIMS/TEM studies. The majority of grains are Mg-rich and amorphous, which is in contrast to astrophysical evidence, which mainly postulate crystalline Mg-rich and amorphous Fe-rich circumstellar condensates. However, the grains might have been rendered amorphous by secondary processes in the ISM or could have condensed under non-equilibrium, low-temperature conditions in the circumstellar outflow. The grains are more likely characterized by a variable, pyroxene-like chemistry, which could be a result of sputtering in the ISM, which preferentially removes Mg. The detected crystalline presolar silicates in this study and in other work are all olivines, whereas grains with a pyroxene stoichiometry are all amorphous except one. This supports astrophysical models which point to different formation pathways for these two types of grains and therefore different crystallinity. However, the relatively high Fe content of three detected presolar olivines in this study and in other work is in contrast to astrophysical evidence and theoretical considerations, which predict essentially Fe-free crystalline grains. It is therefore possible that the infrared spectra might also be compatible with less Mg-rich olivines. The only crystalline presolar silicate with a pyroxene-like stoichiometry is the unusual grain 1_07: although it is chemically enstatite, the electron diffraction pattern could only be indexed to silicate perovskite, which is stable above ~23 GPa. The discovery of a high-pressure phase of presolar origin shows that dust grains encountering interstellar shocks might not necessarily be completely destroyed. In astrophysical models it is in principle also possible that a fraction of larger grains might survive such a shock wave encounter as a high-pressure modification, which is supported by this discovery.
Numerical simulation of flow, H₂SO₄ cycle and new particle formation in the CERN CLOUD chamber
(2011)
To study the effect of galactic cosmic rays on aerosols and clouds, the Cosmic Leaving OUtdoor Droplets (CLOUD) project was established. Experiments are carried out at a 26 m3 tank at CERN (Switzerland). In the experiments, the effect of ionising particle radiation on H2SO4 particle formation and growth is investigated. To evaluate the experimental configuration, the experiment was simulated using a coupled multidimensional CFD – particle model (CLOUD-FPM). In the model the coupled fields of gas/vapour species, temperature, flow velocity and particle properties were computed to investigate the tank's mixing state and mixing times. Simulation results show that the mixing state of the tank's contents largely depends on the characteristics of the mixing fans and a 1-fan configuration, as used in first experiments, may not be sufficient to ensure a homogeneously mixed chamber. To mix the tank properly, 2 fans are necessary. The 1/e response times for instantaneous changes of wall temperature and saturation ratio inside the chamber were found to be in the order of few minutes. Particle nucleation and growth was also simulated and particle number size distribution properties of the freshly nucleated particles (particle number, mean size, standard deviation of the assumed log-normal distribution) were found to be mixed over the tank's volume similar to the gas species.
To study the effect of galactic cosmic rays on aerosols and clouds, the Cosmics Leaving OUtdoor Droplets (CLOUD) project was established. Experiments are carried out at a 26.1 m3 tank at CERN (Switzerland). In the experiments, the effect of ionizing radiation on H2SO4 particle formation and growth is investigated. To evaluate the experimental configuration, the experiment was simulated using a coupled multidimensional computational fluid dynamics (CFD) – particle model. In the model the coupled fields of gas/vapor species, temperature, flow velocity and particle properties were computed to investigate mixing state and mixing times of the CLOUD tank's contents. Simulation results show that a 1-fan configuration, as used in first experiments, may not be sufficient to ensure a homogeneously mixed chamber. To mix the tank properly, two fans and sufficiently high fan speeds are necessary. The 1/e response times for instantaneous changes of wall temperature and saturation ratio were found to be in the order of few minutes. Particle nucleation and growth was also simulated and particle number size distribution properties of the freshly nucleated particles (particle number, mean size, standard deviation of the assumed log-normal distribution) were found to be distributed over the tank's volume similar to the gas species.
Central and western Europe were affected by a compressional tectonic event in the Late Cretaceous, caused by the convergence of Iberia and Europe. Basement uplifts, inverted graben structures, and newly formed marginal troughs are the main expressions of crustal shortening. Although the maximum activity occurred during a short period of time between 90 and 75 Ma, the exact timing of this event is still unclear. Dating of the start and end of Late Cretaceous basin inversion gives very different results depending on the method applied. On the basis of borehole data, facies, and thickness maps, the timing of basin reorganization was reconstructed for several basins in central Europe. The obtained data point to a synchronous start of basin inversion at 95 Ma (Cenomanian), 5 Myr earlier than commonly assumed. The end of the Late Cretaceous compressional event is difficult to pinpoint in central Europe, because regional uplift and salt migration disturb the signal of shifting marginal troughs. Late Campanian to Paleogene strata deposited unconformably on inverted structures indicate slowly declining uplift rates during the latest Cretaceous. The differentiation of separate Paleogene inversion phases in central Europe does not appear possible at present.
Central Europe was affected by a compressional tectonic event in the Late Cretaceous, caused by the convergence of Iberia and Europe. Basement uplifts, inverted graben structures and newly formed marginal troughs are the main expressions of crustal shortening. Although the maximum activity occurred in a short period between 90 and 75 Ma, the exact timing of this event is still unclear. Dating of start and end of basin inversion is very different depending on the applied method. On the basis of borehole data, facies and thickness maps, the timing of basin re-organisation was reconstructed for several basins in Central Europe. The obtained data point to a synchronous start of basin inversion already at 95 Ma (Cenomanian), 5 Million years earlier than commonly assumed. The end of the Late Cretaceous compressional event is more difficult to pinpoint, because regional uplift and salt migration disturb the signal of shifting marginal troughs. Unconformities of Late Campanian to Paleogene age on inverted structures indicate slowly declining uplift rates.
Chlorine monoxide (ClO) plays a key role in stratospheric ozone loss processes at midlatitudes. We present two balloonborne in situ measurements of ClO conducted in northern hemisphere midlatitudes during the period of the maximum of total inorganic chlorine loading in the atmosphere. Both ClO measurements were conducted on board the TRIPLE balloon payload, launched in November 1996 in Le´on, Spain, and in May 1999 in Aire sur l’Adour, France. For both flights a ClO daylight and night time vertical profile could be derived over an altitude range of approximately 15–31 km. ClO mixing ratios are compared to model simulations performed with the photochemical box model version of the Chemical Lagrangian Model of the Stratosphere (CLaMS). Simulations along 24-h backward trajectories were performed to study the diurnal variation of ClO in the midlatitude lower stratosphere. Model simulations for the flight launched in Aire sur l’Adour 1999 show a good agreement with the ClO measurements. For the flight launched in Le´on 1996, a similar good agreement is found, except at around ~ 650 K potential temperature (~26km altitude). However, a tendency is found that for solar zenith angles greater than 86°–87° the simulated ClO mixing ratios substantially overestimate measured ClO by approximately a factor of 2.5 or more for both flights. Therefore we conclude that no indication can be deduced from the presented ClO measurements that substantial uncertainties exist in midlatitude chlorine chemistry of the stratosphere. An exception is the situation at solar zenith angles greater than 86°–87° where model simulations substantial overestimate ClO observations.
Chlorine monoxide (ClO) plays a key role in stratospheric ozone loss processes at midlatitudes. We present two balloon-borne in situ measurements of ClO conducted in northern hemisphere midlatitudes during the period of the maximum of total inorganic chlorine loading in the atmosphere. Both ClO measurements were conducted on board the TRIPLE balloon payload, launched in November 1996 in León, Spain, and in May 1999 in Aire sur l'Adour, France. For both flights a ClO daylight and night-time vertical profile was derived over an altitude range of approximately 15-35 km. ClO mixing ratios are compared to model simulations performed with the photochemical box model version of the Chemical Lagrangian Model of the Stratosphere (CLaMS). Simulations along 24-hour backward trajectories were performed to study the diurnal variation of ClO in the midlatitude lower stratosphere. Model simulations for the flight launched in Aire sur l'Adour 1999 show an excellent agreement with the ClO measurements. For the flight launched in León 1996, an overall good agreement is found, whereas the flight is characterized by a more complex dynamical situation due to a possible mixture of vortex and non-vortex air. We note that for both flights at solar zenith angles greater than 86°-87° simulated ClO mixing ratios are higher than observed ClO mixing ratios. However, the present findings indicate that no substantial uncertainties exist in midlatitude chlorine chemistry of the stratosphere.
Modelling short-term variability in carbon and water exchange in a temperate Scots pine forest
(2015)
The vegetation–atmosphere carbon and water exchange at one particular site can strongly vary from year to year, and understanding this interannual variability in carbon and water exchange (IAVcw) is a critical factor in projecting future ecosystem changes. However, the mechanisms driving this IAVcw are not well understood. We used data on carbon and water fluxes from a multi-year eddy covariance study (1997–2009) in a Dutch Scots pine forest and forced a process-based ecosystem model (Lund–Potsdam–Jena General Ecosystem Simulator; LPJ-GUESS) with local data to, firstly, test whether the model can explain IAVcw and seasonal carbon and water exchange from direct environmental factors only. Initial model runs showed low correlations with estimated annual gross primary productivity (GPP) and annual actual evapotranspiration (AET), while monthly and daily fluxes showed high correlations. The model underestimated GPP and AET during winter and drought events. Secondly, we adapted the temperature inhibition function of photosynthesis to account for the observation that at this particular site, trees continue to assimilate at very low atmospheric temperatures (up to daily averages of −10 °C), resulting in a net carbon sink in winter. While we were able to improve daily and monthly simulations during winter by lowering the modelled minimum temperature threshold for photosynthesis, this did not increase explained IAVcw at the site. Thirdly, we implemented three alternative hypotheses concerning water uptake by plants in order to test which one best corresponds with the data. In particular, we analyse the effects during the 2003 heatwave. These simulations revealed a strong sensitivity of the modelled fluxes during dry and warm conditions, but no single formulation was consistently superior in reproducing the data for all timescales and the overall model–data match for IAVcw could not be improved. Most probably access to deep soil water leads to higher AET and GPP simulated during the heatwave of 2003. We conclude that photosynthesis at lower temperatures than assumed in most models can be important for winter carbon and water fluxes in pine forests. Furthermore, details of the model representations of water uptake, which are often overlooked, need further attention, and deep water access should be treated explicitly.
Modelling short-term variability in carbon and water exchange in a temperate Scots pine forest
(2015)
The vegetation–atmosphere carbon and water exchange at one particular site can strongly vary from year to year, and understanding this interannual variability in carbon and water exchange (IAVcw) is a critical factor in projecting future ecosystem changes. However, the mechanisms driving this IAVcw are not well understood. We used data on carbon and water fluxes from a multi-year eddy covariance study (1997–2009) in a Dutch Scots pine forest and forced a process-based ecosystem model (Lund–Potsdam–Jena General Ecosystem Simulator; LPJ-GUESS) with local data to, firstly, test whether the model can explain IAVcw and seasonal carbon and water exchange from direct environmental factors only. Initial model runs showed low correlations with estimated annual gross primary productivity (GPP) and annual actual evapotranspiration (AET), while monthly and daily fluxes showed high correlations. The model underestimated GPP and AET during winter and drought events. Secondly, we adapted the temperature inhibition function of photosynthesis to account for the observation that at this particular site, trees continue to assimilate at very low atmospheric temperatures (up to daily averages of −10 °C), resulting in a net carbon sink in winter. While we were able to improve daily and monthly simulations during winter by lowering the modelled minimum temperature threshold for photosynthesis, this did not increase explained IAVcw at the site. Thirdly, we implemented three alternative hypotheses concerning water uptake by plants in order to test which one best corresponds with the data. In particular, we analyse the effects during the 2003 heatwave. These simulations revealed a strong sensitivity of the modelled fluxes during dry and warm conditions, but no single formulation was consistently superior in reproducing the data for all timescales and the overall model–data match for IAVcw could not be improved. Most probably access to deep soil water leads to higher AET and GPP simulated during the heatwave of 2003. We conclude that photosynthesis at lower temperatures than assumed in most models can be important for winter carbon and water fluxes in pine forests. Furthermore, details of the model representations of water uptake, which are often overlooked, need further attention, and deep water access should be treated explicitly.
Analysing the composition of ambient ultrafine particles (UFPs) is a challenging task due to the low mass and chemical complexity of small particles, yet it is a prerequisite for the identification of particle sources and the assessment of potential health risks. Here, we show the molecular characterization of UFPs, based on cascade impactor (Nano-MOUDI) samples that were collected at an air quality monitoring station near one of Europe's largest airports, in Frankfurt, Germany. At this station, particle-size-distribution measurements show an enhanced number concentration of particles smaller than 50 nm during airport operating hours. We sampled the lower UFP fraction (0.010–0.018, 0.018–0.032, 0.032–0.056 µm) when the air masses arrived from the airport. We developed an optimized filter extraction procedure using ultra-high-performance liquid chromatography (UHPLC) for compound separation and a heated electrospray ionization (HESI) source with an Orbitrap high-resolution mass spectrometer (HRMS) as a detector for organic compounds. A non-target screening detected ∼200 organic compounds in the UFP fraction with sample-to-blank ratios larger than 5. We identified the largest signals as homologous series of pentaerythritol esters (PEEs) and trimethylolpropane esters (TMPEs), which are base stocks of aircraft lubrication oils. We unambiguously attribute the majority of detected compounds to jet engine lubrication oils by matching retention times, high-resolution and accurate mass measurements, and comparing tandem mass spectrometry (MS2) fragmentation patterns between both ambient samples and commercially available jet oils. For each UFP stage, we created molecular fingerprints to visualize the complex chemical composition of the organic fraction and their average carbon oxidation state. These graphs underline the presence of the homologous series of PEEs and TMPEs and the appearance of jet oil additives (e.g. tricresyl phosphate, TCP). Targeted screening of TCP confirmed the absence of the harmful tri-ortho isomer, while we identified a thermal transformation product of TMPE-based lubrication oil (trimethylolpropane phosphate, TMP-P). Even though a quantitative determination of the identified compounds is limited, the presented method enables the qualitative detection of molecular markers for jet engine lubricants in UFPs and thus strongly improves the source apportionment of UFPs near airports.
Analysing the composition of ambient ultrafine particles (UFP) is a challenging task due to the low mass and chemical complexity of small particles, yet it is a prerequisite for the identification ofparticle sources and the assessment of potential health risks. Here, we show the molecular characterization of UFP, based on cascade impactor (Nano-MOUDI) 10samples that were collected at an air quality monitoring station nearby one of Europe`s largest airports in Frankfurt, Germany. At this station, particle-size-distribution measurements show enhanced number concentration of particles smaller than 50nm during airport operating hours. We sampled the lower UFP fraction (0.010-0.018 μm; 0.018-0.032 μm; 0.032-0.056 μm) when the air masses arrived from the airport. We developed an optimized filter extraction procedure, used ultra-high performance liquid chromatography (UHPLC) for compound separation, and a heated electrospray ionization (HESI) source with an 15Orbitrap high-resolution mass spectrometer (HRMS) as a detector for organic compounds. A non-target screening detected ~200 organic compounds in the UFP fraction with sample-to-blank ratios larger than five. We identified the largest signals as homologous series of pentaerythritol esters (PEE) and trimethylolpropane esters (TMPE), which are base stocks of aircraft lubrication oils. We unambiguously attribute the majority of detected compounds to jet engine lubrication oils by matching retention times, high-resolution/accurate mass (HR/AM) measurements, and comparing MS/MS fragmentation patterns between both ambient samples and commercially available jet oils. For each UFP stage, we created molecular fingerprints to visualize the complex chemical composition ofthe organic fraction and their average carbon oxidation state. These graphs underline the presence of the homologous series of PEE and TMPE, and the appearance of jet oil additives (e.g. tricresyl phosphate (TCP)). Targeted screening on TCP confirmed the absence of the harmful tri-orthoisomer, while we identified a thermal transformation product of TMPE-based lubrication oil (trimethylolpropane phosphate (TMP-P)). Even though a quantitative determination of the identified compounds is limited, the presented method enables the qualitative detection of molecular markers for jet engine lubricants in UFP and thus strongly improves the source apportionment of UFP near airports.
As part of two drilling campaigns of the International Continental Scientific Drilling Program (ICDP), several geophysical borehole measurements were carried out by the Leibniz Institute for Applied Geophysics (LIAG) in two lakes. The acquired data was used to answer stratigraphic and paleoclimatic research questions, including the establishment of robust age-depth models and the construction of continuous lithological profiles.
Lake Towuti is located on Sulawesi (Indonesia), within the "Indo-Pacific Warm Pool" (IPWP), a globally important region for atmospheric heat and moisture budgets. The lake exists for approximately one million years, but its exact age is uncertain. We present the first agedepth model for the approximately 100 m continuous sediment sequence from the central part of the lake. The basis for this model is the magnetic susceptibility measured in the borehole and a tephra layer with an age of about 797 ka at 72 m depth. Our age-depth model is inferred from cyclostratigraphic analysis of borehole data and covers a period from 903 ± 11 to 131 ± 67 ka. We suggest that orbital eccentricity and/or changes between global cold and warm periods are responsible for hydroclimatic changes in the IPWP, that these changes affect sedimentation processes in Lake Towuti, and that we can measure and observe this effect in the sediment properties today. Additionally, we created a continuous artificial lithological profile from a series of different borehole data using cluster analysis. This provides information from parts of the borehole where no sediment is available due to core loss.
Lake Ohrid is 1.36 million years old and is located on the Balkan Peninsula on the border between Albania and North Macedonia. The primary hole 'DEEP' in the central part of the lake has been the subject of several investigations, but information about sediments of the marginal locations 'Pestani' and 'Cerava' have not been published yet. In our study, we use natural gamma radiation (GR) measured in the borehole to generate an age-depth model for DEEP. This is performed using the correlation of GR to the global LR04 reference record of Lisiecki and Raymo (2005).
The age information is then transferred via prominent seismic marker horizons to the other two sites, Pestani and Cerava, where it provides the first age-control points for the construction of age-depth models from correlation of GR to LR04. The generated age-depth models are tested using cyclostratigraphic methods, but the limits of this approach are revealed. At DEEP, sedimentation rates (SR) from the cyclostratigraphic method and the correlative approach differ by 2.8 %, at Pestani this difference is 16.7 %, and at Cerava the quality of the data does not allow a reliable evaluation of SR using the cyclostratigraphic approach. We used cluster analysis to construct artificial lithological profiles at all three sites and integrated them into the respective age-depth models. This enables us to determine which sediment types were deposited at what time, and we recognize the change between warm and cold periods in the sediment properties at all three locations. The analyses in this study were all performed on borehole and seismic data and thus do not involve sediment core data. Especially at Pestani and Cerava, new insights into the sedimentological history of Lake Ohrid could be obtained.
In the last part we discuss the occurrence of the half-precession (HP) signal in the European region during the last one million years. The focus is on Lake Ohrid, but a range of other proxies, from the eastern Mediterranean, across the European continent, up to Greenland are analyzed in regards to HP. Applying filters, we focus on the frequency range with a period of 13-8.5 ka and only HP remains in the records. We use correlative methods to determine the clarity of the HP signal in proxies distributed across the European realm. Additionally, we determined the development of HP over time. The HP signal is clearest in the southeast and decreases toward the north. It is further more pronounced in interglacial periods and in the younger part (<621 ka) of most proxies. We suggest that there are mechanisms that transmit the HP signal from its origin near the equator to higher latitudes via different processes. In this context, for instance, the African monsoon, the Nile River and the Mediterranean outflow via the Strait of Gibraltar can be important factors.
Over the last several decades, spinel-structured minerals with the chemical formula AB2O4 (where A and B stand for divalent and trivalent cations, respectively) have attracted more and more attention, particularly with regards to their breakdown at high pressures and temperatures and the nature of the so-called "post-spinel" phases. Spinel-structured phases with different endmember compositions, like magnetite (Fe3O4), hercynite (FeAl2O4) or spinel (MgAl2O4), are known to breakdown differently at high pressure-temperature conditions (e.g., Akaogi et al. 1999; Schollenbruch et al. 2010; Woodland et al. 2012). Such phases are of particular interest when they incorporate ferric (Fe3+) and ferrous (Fe2+) cations as this makes their stability sensitive to redox conditions. Since magnetite and magnesioferrite (MgFe3+ 2O4) have been found as inclusions in diamond (e.g., Stachel et al. 1998; Harte et al. 1999; Wirth et al. 2014; Palot et al. 2016; Jacob et al. 2016), understanding their phase relations is important for setting constraints on the conditions of their formation.
This study aimed to experimentally investigate the phase relations of Fe-Mg spinel-structured phases at conditions of the deep upper mantle and transition zone. Exploring the stability of new post-spinel phases and their characterization were also major goals of this study. Approaching a pyrolitic mantle composition by adding amounts of SiO2 in the system allowed constraints on the relevance of Fe-Mg post-spinel phases coexisting with mantle silicates to be made. ...
Long-term average groundwater recharge representing the sustainable groundwater resources is modeled as a 0.5° by 0.5° grid on global scale by the WaterGAP Global Hydrology Model. Due to uncertainties of estimating groundwater recharge, especially in semiarid and arid regions, independent estimates are used for calibrating the model. This work compiled a new set of independent groundwater recharge estimates based on a work of Scanlon et al. (2006). The 59 independent estimates, together with an already existing independent estimates compilation, are used for the evaluation of two WGHM variants; one variant is modeling with an improved more realistically distributed daily precipitation dataset.
The objective of this thesis is the evaluation of the modeled data of the WaterGAP Global Hydrology Model (WGHM). The analysis of the impact of the new Watch Forcing Data (WFD) precipitation dataset on the modeled groundwater recharge tends to result in lower values in humid and higher values in (semi-)arid regions compared to the WGHM standard variant. Comparing both WGHM variants to the independent estimates compilations, representing (semi-)arid regions, the WGHM variant shows over- and underestimations especially of the low values and the WGHM WFD variant shows a bias toward overestimation especially for values below 4 mm/yr. The analysis of texture, hydrogeology and vegetation/ land cover could not give satisfying explanations for the discrepancies, but derived from the groundwater recharge measurement methods analysis indirect/ localized recharge seems to be a significant factor causing underestimations, as resulted in the comparison of the independent estimates based on Scanlon et al. 2006 with the WGHM variants.
Derivation and characterization of a new filter for nonlinear high-dimensional data assimilation
(2015)
Data assimilation (DA) combines model forecasts with real-world observations to achieve an optimal estimate of the state of a dynamical system. The quality of predictions in nonlinear and chaotic systems such as atmospheric or oceanic circulation is strongly sensitive to the initial conditions. Therefore, beyond the consistent reconstruction of past states, a primary relevance of advanced DA methods concerns the proper model initialization. The ensemble Kalman filter (EnKF) and its deterministic variants, mostly square root filters such as the ensemble transform Kalman filter (ETKF), represent a popular alternative to variational DA schemes. They are applied in a wide range of research and operations. Their forecast step employs an ensemble integration that fully respects the nonlinear nature of the analyzed system. In the analysis step, they implicitly assume the prior state and observation errors to be Gaussian. Consequently, in nonlinear systems, the mean and covariance of the analysis ensemble are biased and these filters remain suboptimal. In contrast, the fully nonlinear, non-Gaussian particle filter (PF) relies on Bayes' theorem without further assumptions, which guarantees an exact asymptotic behavior. However, it is exposed to weight collapse, particularly in higher-dimensional settings, known as the curse of dimensionality.
This work presents a new method to obtain an analysis ensemble with mean and covariance that exactly match the corresponding Bayesian estimates. This is achieved by a deterministic matrix square root transformation of the forecast ensemble, and subsequently a suitable random rotation that significantly contributes to filter stability while preserving the required second-order statistics. The forecast step remains as in the ETKF. The algorithm, which is fairly easy to implement and computationally efficient, is referred to as the nonlinear ensemble transform filter (NETF). The limitation with respect to fully-nonlinear filtering is that the NETF only considers the mean and covariance of the Bayesian analysis density, neglecting higher-order moments.
The properties and performance of the proposed algorithm are investigated via a set of experiments. The results indicate that such a filter formulation can increase the analysis quality, even for relatively small ensemble sizes, compared to other ensemble filters in nonlinear, non-Gaussian scenarios. They also confirm that localization enhances the applicability of this PF-inspired scheme in larger-dimensional systems. Finally, the novel filter is coupled to a large-scale ocean general circulation model with a realistic observation scenario. The NETF remains stable with a small ensemble size and shows a consistent behavior. Additionally, its analyses exhibit low estimation errors, as revealed by a comparison with a free ensemble integration and the ETKF. The results confirm that, in principle, the filter can be applied successfully and as simple as the ETKF in high-dimensional problems. No further modifications are needed, even though the algorithm is only based on the particle weights. Thus, it is able to overcome the curse of dimensionality, even in deterministic systems. This proves that the NETF constitutes a promising and user-friendly method for nonlinear high-dimensional DA.
Das Klima, insbesondere der Niederschlag ist einer der wichtigsten natürlichen Gestaltungsfaktoren für die Savannenregion Westafrikas. Morphodynamik, Bodenbildung, Abflußregime sowie Wasserhaushalt werden direkt vom Klima bestimmt. Der Niederschlag ist zudem das begrenzende Element für das Wachstum von Flora und Fauna. Jede Änderung der Niederschlagsmenge hat gravierende Folgen für die Landschaft und seine Bewohner. Die Untersuchung langfristiger klimatischer Veränderungen ist ein Beitrag die Entstehung und den Wandel der Landschaft zu verstehen. Hierdurch können parallele Entwicklungen zwischen Natur- und Kulturraum im langfristigen Zusammenhängen gesehen werden. Ziel ist, das Klima des Tschadseegebietes seit dem Beginn regelmäßiger Aufzeichnung von Klimadaten mit Hilfe verschiedener statistischer Verfahren zu beschreiben. Des weiteren sollen Wechselwirkungen und Zusammenhänge zu externen Faktoren (Globale Zirkulation, Ozeantemperatur, Solarstrahlung,...) aufgezeigt werden.
Über gewundene Bergkrystalle
(1894)
About half of present-day cloud condensation nuclei originate from atmospheric nucleation, frequently appearing as a burst of new particles near midday1. Atmospheric observations show that the growth rate of new particles often accelerates when the diameter of the particles is between one and ten nanometres2,3. In this critical size range, new particles are most likely to be lost by coagulation with pre-existing particles4, thereby failing to form new cloud condensation nuclei that are typically 50 to 100 nanometres across. Sulfuric acid vapour is often involved in nucleation but is too scarce to explain most subsequent growth5,6, leaving organic vapours as the most plausible alternative, at least in the planetary boundary layer7,8,9,10. Although recent studies11,12,13 predict that low-volatility organic vapours contribute during initial growth, direct evidence has been lacking. The accelerating growth may result from increased photolytic production of condensable organic species in the afternoon2, and the presence of a possible Kelvin (curvature) effect, which inhibits organic vapour condensation on the smallest particles (the nano-Köhler theory)2,14, has so far remained ambiguous. Here we present experiments performed in a large chamber under atmospheric conditions that investigate the role of organic vapours in the initial growth of nucleated organic particles in the absence of inorganic acids and bases such as sulfuric acid or ammonia and amines, respectively. Using data from the same set of experiments, it has been shown15 that organic vapours alone can drive nucleation. We focus on the growth of nucleated particles and find that the organic vapours that drive initial growth have extremely low volatilities (saturation concentration less than 10−4.5 micrograms per cubic metre). As the particles increase in size and the Kelvin barrier falls, subsequent growth is primarily due to more abundant organic vapours of slightly higher volatility (saturation concentrations of 10−4.5 to 10−0.5 micrograms per cubic metre). We present a particle growth model that quantitatively reproduces our measurements. Furthermore, we implement a parameterization of the first steps of growth in a global aerosol model and find that concentrations of atmospheric cloud concentration nuclei can change substantially in response, that is, by up to 50 per cent in comparison with previously assumed growth rate parameterizations.
Für eine möglichst vollständige analytische Beschreibung werden in der statistischen Klimatologie beobachtete Klimazeitreihen als Realisation eines stochastischen Prozesses, das heißt als eine Folge von Zufallsvariablen verstanden. Die Zeitreihe soll im wesentlichen durch eine analytische Funktion der Zeit beschrieben werden können und die Beobachtung nur durch Zufallseinflüsse von dieser Funktion abweichen. Diese analytische Funktion setzt sich aus der Summe zeitlich strukturierter Komponenten zusammen, welche aus klimatologischem Blickwinkel interpretierbar erscheinen. Es werden Funktionen zugelassen, die den Jahresgang, Trends, episodische Komponenten und deren Änderung beschreiben. Die Extremereignisse sind als eine besondere weitere Komponente in die Zeitreihenanalyse aufgenommen und als von Änderungen in den Parametern der Verteilung unabhängige, extreme Werte definiert. Die Zufallseinflüsse sollen zunächst als Realisierungen unabhängiger normalverteilter Zufallsvariablen mit dem Erwartungswert Null und im Zeitablauf konstanter Varianz interpretiert werden können. In diesem Fall beschreibt die analytische Funktion der Zeit, die Summe detektierter strukturierter Komponenten, den zeitlichen Verlauf des Mittels. Ein zu einem bestimmten Zeitpunkt tatsächlich beobachteter Wert kann dann als eine mögliche Realisation einer Zufallsvariablen interpretiert werden, die der Gaußverteilung mit dem Mittelwert µ(t) zur Zeit t und konstanter Varianz genügt. Da die zugrundeliegenden Annahmen, unter Verwendung klimatologisch interpretierbarer Basisfunktionen, in der Analyse von Klimazeitreihen, die nicht die Temperatur betreffen, zumeist nicht erfüllt sind, wird in eine Verallgemeinerung des Konzepts der Zeitreihenzerlegung in einen deterministischen und einen statistischen Anteil eingeführt. Zeitlich strukturierte Änderungen werden nun in verschiedenen Verteilungsparametern frei wählbarer Wahrscheinlichkeitsdichtefunktionen gesucht. Die gängige Beschränkung auf die Schätzung einer zeitlich veränderlichen Lokation wird aufgehoben. Skalenschätzer sowie Schätzer fär den Formparameter spielen ebenso relevante Rollen fär die Beschreibung beobachteter Klimavariabilität. Die Klimazeitreihen werden wieder als Realisation eines Zufallprozesses verstanden, jedoch genügen die Zufallsvariablen nun einer frei wählbaren Wahrscheinlichkeitsdichtefunktion. Die zeitlich strukturierten Änderungen in den Verteilungsparametern werden auf Basis der gesamten Zeitreihe für jeden Zeitpunkt geschätzt. Die aus der Analyse resultierende analytische Beschreibung in Form einer zeitabhängigen Wahrscheinlichkeitsdichtefunktion ermöglicht weiterhin die Schätzung von Über- und Unterschreitungswahrscheinlichkeiten beliebig wählbarer Schwellenwerte für jeden Zeitpunkt des Beobachtungszeitraums. Diese Methode erlaubt insbesondere eine statistische Modellierung monatlicher Niederschlagsreihen durch die Zerlegung in einen deterministischen und einen statistischen Anteil. In dem speziellen Fall von 132 Reihen monatlicher Niederschlagssummen deutscher Stationen 1901-2000 gelingt eine vollständige analytische Beschreibung der Reihen durch ihre Interpretation als Realisation einer Gumbel-verteilten Zufallsvariablen mit variablem Lage- und Streuparameter. Auf Basis der gewonnenen analytischen Beschreibung der Reihen kann beispielsweise im Westen Deutschlands auf Verschiebungen der jährlichen Überschreitungsmaxima des 95%-Perzentils von den Sommer- in die Wintermonate geschlossen werden. Sie werden durch relativ starke Anstiege in der Überschreitungswahrscheinlichkeit (bis 10%) in den Wintermonaten und nur geringe Zunahmen oder aber Abnahmen in den Sommermonaten hervorgerufen. Dies geht mit einer Zunahme der Unterschreitungswahrscheinlichkeit in den Winter- und einer Abnahme in den Sommermonaten einher. Monte-Carlo-Simulationen zeigen, daß jahreszeitlich differenzierte Schätzungen von Änderungen im Erwartungswert, also gebräuchliche Trends, auf Basis der Kleinst-Quadrate-Methode systematischen Bias und hohe Varianz aufweisen. Eine Schätzung der Trends im Mittel auf Basis der statistischen Modellierung ist somit ebenso den Kleinst-Quadrate-Schätzern vorzuziehen. Hinsichtlich der Niederschlagsanalysen stellen jedoch aride Gebiete, mit sehr seltenen Niederschlägen zu bestimmten Jahreszeiten, die Grenze der Methode dar, denn zu diesen Zeitpunkten ist eine vertrauenswürdige Schätzung einer Wahrscheinlichkeitsdichtefunktion nicht möglich. In solchen Fällen ist eine grundsätzlich andere Herangehensweise zur Modellierung der Reihen erforderlich.
Für eine möglichst vollständige analytische Beschreibung werden in der statistischen Klimatologie beobachtete Klimazeitreihen als Realisation eines stochastischen Prozesses, das heißt als eine Folge von Zufallsvariablen verstanden. Die Zeitreihe soll im wesentlichen durch eine analytische Funktion der Zeit beschrieben werden können und die Beobachtung nur durch Zufallseinflüsse von dieser Funktion abweichen. Diese analytische Funktion setzt sich aus der Summe zeitlich strukturierter Komponenten zusammen, welche aus klimatologischem Blickwinkel interpretierbar erscheinen. Es werden Funktionen zugelassen, die den Jahresgang, Trends, episodische Komponenten und deren Änderung beschreiben. Die Extremereignisse sind als eine besondere weitere Komponente in die Zeitreihenanalyse aufgenommen und als von Änderungen in den Parametern der Verteilung unabhängige, extreme Werte definiert. Die Zufallseinflüsse sollen zunächst als Realisierungen unabhängiger normalverteilter Zufallsvariablen mit dem Erwartungswert Null und im Zeitablauf konstanter Varianz interpretiert werden können. In diesem Fall beschreibt die analytische Funktion der Zeit, die Summe detektierter strukturierter Komponenten, den zeitlichen Verlauf des Mittels. Ein zu einem bestimmten Zeitpunkt tatsächlich beobachteter Wert kann dann als eine mögliche Realisation einer Zufallsvariablen interpretiert werden, die der Gaußverteilung mit dem Mittelwert µ(t) zur Zeit t und konstanter Varianz genügt. Da die zugrundeliegenden Annahmen, unter Verwendung klimatologisch interpretierbarer Basisfunktionen, in der Analyse von Klimazeitreihen, die nicht die Temperatur betreffen, zumeist nicht erfüllt sind, wird in eine Verallgemeinerung des Konzepts der Zeitreihenzerlegung in einen deterministischen und einen statistischen Anteil eingeführt. Zeitlich strukturierte Änderungen werden nun in verschiedenen Verteilungsparametern frei wählbarer Wahrscheinlichkeitsdichtefunktionen gesucht. Die gängige Beschränkung auf die Schätzung einer zeitlich veränderlichen Lokation wird aufgehoben. Skalenschätzer sowie Schätzer fär den Formparameter spielen ebenso relevante Rollen fär die Beschreibung beobachteter Klimavariabilität. Die Klimazeitreihen werden wieder als Realisation eines Zufallprozesses verstanden, jedoch genügen die Zufallsvariablen nun einer frei wählbaren Wahrscheinlichkeitsdichtefunktion. Die zeitlich strukturierten Änderungen in den Verteilungsparametern werden auf Basis der gesamten Zeitreihe für jeden Zeitpunkt geschätzt. Die aus der Analyse resultierende analytische Beschreibung in Form einer zeitabhängigen Wahrscheinlichkeitsdichtefunktion ermöglicht weiterhin die Schätzung von Über- und Unterschreitungswahrscheinlichkeiten beliebig wählbarer Schwellenwerte für jeden Zeitpunkt des Beobachtungszeitraums. Diese Methode erlaubt insbesondere eine statistische Modellierung monatlicher Niederschlagsreihen durch die Zerlegung in einen deterministischen und einen statistischen Anteil. In dem speziellen Fall von 132 Reihen monatlicher Niederschlagssummen deutscher Stationen 1901-2000 gelingt eine vollständige analytische Beschreibung der Reihen durch ihre Interpretation als Realisation einer Gumbel-verteilten Zufallsvariablen mit variablem Lage- und Streuparameter. Auf Basis der gewonnenen analytischen Beschreibung der Reihen kann beispielsweise im Westen Deutschlands auf Verschiebungen der jährlichen Überschreitungsmaxima des 95%-Perzentils von den Sommer- in die Wintermonate geschlossen werden. Sie werden durch relativ starke Anstiege in der Überschreitungswahrscheinlichkeit (bis 10%) in den Wintermonaten und nur geringe Zunahmen oder aber Abnahmen in den Sommermonaten hervorgerufen. Dies geht mit einer Zunahme der Unterschreitungswahrscheinlichkeit in den Winter- und einer Abnahme in den Sommermonaten einher. Monte-Carlo-Simulationen zeigen, daß jahreszeitlich differenzierte Schätzungen von Änderungen im Erwartungswert, also gebräuchliche Trends, auf Basis der Kleinst-Quadrate-Methode systematischen Bias und hohe Varianz aufweisen. Eine Schätzung der Trends im Mittel auf Basis der statistischen Modellierung ist somit ebenso den Kleinst-Quadrate-Schätzern vorzuziehen. Hinsichtlich der Niederschlagsanalysen stellen jedoch aride Gebiete, mit sehr seltenen Niederschlägen zu bestimmten Jahreszeiten, die Grenze der Methode dar, denn zu diesen Zeitpunkten ist eine vertrauenswürdige Schätzung einer Wahrscheinlichkeitsdichtefunktion nicht möglich. In solchen Fällen ist eine grundsätzlich andere Herangehensweise zur Modellierung der Reihen erforderlich.
Die konventionelle Extremwertstatistik die sich an der Über- bzw. Unterschreitungshäufigkeit bestimmter Schwellenwerte orientiert, beinhaltet den Nachteil, daß Änderungen der Parameter der Häufigkeitsverteilung die Extremwertwahrscheinlichkeit beeinflussen. So kann allein das Vorhandensein eines Trends für derartige Veränderungen verantwortlich sein. Die hier gewählte Methodik vermeidet diesen Nachteil, indem sie eine Zerlegung der betrachteten Zeitreihen in einen strukturierten und einen unstrukturierten Anteil durchführt. Dabei setzt sich der strukturierte Anteil aus einer Trend-, Saison- und glatten Komponente zusammen. Aus der Summe dieser in der Zeitreihe signifikant enthaltenen Komponenten läßt sich die Eintrittswahrscheinlichkeit von Extremwerten ableiten. Ähnliches gilt für den unstrukturierten Anteil insbesondere für die Varianz des Residuums. Das Residuum kann aber auch Werte enthalten, die nicht zu ihrer ansonsten angepaßten Häufigkeitsverteilung passen. Solche Werte werden als Extremereignisse bezeichnet und sind von den Extremwerten zu unterschieden. In der vorliegenden Arbeit werden nun, getrennt voneinander, durch Änderungen in den Parametern der Häufigkeitsverteilung hervorgerufene Variationen der Extremwertwahrscheinlichkeit als auch parameterunabhängige Extremereignisse der bodennahen Lufttemperatur betrachtet. Als Datenbasis dienten 41, wahrscheinlich homogene, europäische Stationszeitreihen von Monatsmitteltemperaturen, die den Zeitraum von 1871 bis 1990 abdecken. In den untersuchten Temperaturzeitreihen wurde an 37 von 41 Stationen ein positiver Trend detektiert, woraus ein Anstieg der Extremwertwahrscheinlichkeit mit der Zeit resultiert. Die glatten, niederfrequenten Schwingungen wirken sich in den meisten Fällen um 1890 und 1975 negativ und um 1871, 1940 und 1990 positiv auf die Extremwertwahrscheinlich keit aus. Desweiteren treten Änderungen in der Saisonfigur bezüglich der Amplitude und der Phasenlage auf. Detektierte Zunahmen in der Amplitude des Jahresgangs führen zu einer positiven Änderung der Extremwertwahrscheinlichkeit. Signifikante Änderungen in der Phasenlage der Saisonfigur erzeugen in den Anomaliezeitreihen einen saisonal unterschiedlichen Trend, dessen Amplitude, in den betrachteten Fällen, in der Größenordnung der Trendkomponente liegt. Saisonal unterschiedliche Trends beeinflussen saisonal unterschiedlich die Wahrscheinlichkeit für das Eintreten von Extremwerten. Die Residuen von fünf Temperaturzeitreihen weisen signifikante Varianzinstationaritäten auf, wobei in nur einem Fall die Varianz mit der Zeit zunimmt und somit einen Anstieg der Extremwertwahrscheinlichkeit erzeugt. Extremereignisse treten vorwiegend in Form besonders kalter Winter auf und können wahrscheinlich als Realisation eines Poisson-Prozesses interpretiert werden. Sie erscheinen zufällig über den Beobachtungszeitraum verteilt mit einer mittleren Wiederkehrzeit von mehr als 10 Jahren.
Ecophysiological studies on Antarctic cryptophytes to assess whether climatic changes such as ocean acidification and enhanced stratification affect their growth in Antarctic coastal waters in the future are lacking so far. This is the first study that investigated the combined effects of increasing availability of pCO2 (400 and 1000 µatm) and irradiance (20, 200 and 500 μmol photons m−2 s −1) on growth, elemental composition and photophysiology of the Antarctic cryptophyte Geminigera cryophila. Under ambient pCO2, this species was characterized by a pronounced sensitivity to increasing irradiance with complete growth inhibition at the highest light intensity. Interestingly, when grown under high pCO2 this negative light effect vanished and it reached highest rates of growth and particulate organic carbon production at the highest irradiance compared to the other tested experimental conditions. Our results for G. cryophila reveal beneficial effects of ocean acidification in conjunction with enhanced irradiance on growth and photosynthesis. Hence, cryptophytes such as G. cryophila may be potential winners of climate change, potentially thriving better in more stratified and acidic coastal waters and contributing in higher abundance to future phytoplankton assemblages of coastal Antarctic waters.
Reliable identification of chondrules, calcium-aluminum-rich inclusions (CAIs), carbonate grains, and Ca-phosphate grains at depth within untouched, unprepared chondritic samples by a nondestructive analytical method, such as synchrotron X-ray fluorescence (SXRF) computed tomography (CT), is an essential first step before intrusive analytical and sample preparation methods are performed. The detection of a local Ca-enrichment could indicate the presence of such a component, all of which contain Ca as major element and/or Ca-bearing minerals, allowing it to be precisely located at depth within a sample. However, the depth limitation from which Ca-K fluorescence can travel through a chondrite sample (e.g., ∼115 µm through material of 1.5 g cm−3) to XRF detectors leaves many Ca-bearing components undetected at deeper depths. In comparison, Sr-K lines travel much greater distances (∼1700 µm) through the same sample density and are, thus, detected from much greater depths. Here, we demonstrate a clear, positive, and preferential correlation between Ca and Sr and conclude that Sr-detection can be used as proxy for the presence of Ca (and, thus, Ca-bearing components) throughout mm-sized samples of carbonaceous chondritic material. This has valuable implications, especially for sample return missions from carbonaceous C-type asteroids, such as Ryugu or Bennu. Reliable localization, identification, and targeted analysis by SXRF of Ca-bearing chondrules, CAIs, and carbonates at depth within untouched, unprepared samples in the initial stages of a multianalysis investigation insures the valuable information they hold of pre- and post-accretion processes in the early solar system is neither corrupted nor destroyed in subsequent processing and analyses.
Chemical ozone loss in winter 1991–1992 is recalculated based on observations of the HALOE satellite instrument, ER-2 aircraft measurements and balloon data. HALOE satellite observations are shown to be reliable in the lower stratosphere below 400 K, at altitudes where profiles are most likely disturbed by the enhanced sulfate aerosols, as a result of the Mt. Pinatubo eruption in June 1991. Very large chemical ozone loss was observed below 400 K from Kiruna balloon observations between December and March 1992. Additionally, for the two winters after the Mt. Pinatubo eruption, HALOE satellite observations show a stronger extent of chemical ozone loss at lower altitudes compared to other Arctic winter between 1991 and 2003. In stipe of already occurring deactivation of chlorine in March 1992, Mipas-B and LPMA balloon observations indicate still chlorine activation at lower altitudes, consistent with observed chemical ozone loss occurring between February and March and April. Enhanced chemical ozone loss in the Arctic winter 1991–1992 as calculated in earlier studies is corroborated here.
Chemical ozone loss in winter 1991–1992 is recalculated based on observations of the HALOE satellite instrument, Version 19, ER-2 aircraft measurements and balloon data. HALOE satellite observations are shown to be reliable in the lower stratosphere below 400 K, at altitudes where the measurements are most likely disturbed by the enhanced sulfate aerosol loading, as a result of the Mt.~Pinatubo eruption in June 1991. Significant chemical ozone loss (13–17 DU) is observed below 380 K from Kiruna balloon observations and HALOE satellite data between December 1991 and March 1992. For the two winters after the Mt. Pinatubo eruption, HALOE satellite observations show a stronger extent of chemical ozone loss towards lower altitudes compared to other Arctic winters between 1991 and 2003. In spite of already occurring deactivation of chlorine in March 1992, MIPAS-B and LPMA balloon observations indicate that chlorine was still activated at lower altitudes, consistent with observed chemical ozone loss occurring between February and March and April. Large chemical ozone loss of more than 70 DU in the Arctic winter 1991–1992 as calculated in earlier studies is corroborated here.
In dieser Arbeit wurde der chemische Ozonverlust in der arktischen Stratosphäre über elf Jahre hinweg, zwischen 1991 und 2002, mit Hilfe der so genannten "Ozon-Tracer Korrelationstechnik" (TRAC), untersucht. Bei dieser Methode werden Korrelationen zwischen Ozon und langlebigen Spurenstoffen im Verlauf des Winters im Polarwirbels beobachtet und so der jährliche akkumulierte Ozonverlust berechnet. Die Ergebnisse dieser Arbeit basieren im wesentlichen auf Messdaten der Satelliteninstrumente: HALOE (Halogen Occultation Experiment) auf UARS (Upper Atmosphere Research Satellite) und ILAS (Improved Limb Atmospheric Spectrometer) Instrument auf ADEOS (Advanced Earth Observing Satellite). Das HALOE Instrument misst seit Oktober 1991 kontinuierlich alle zwei bis drei Monate für einige Tage in höheren nördlichen Breiten. ILAS lieferte ausschließlich für den Winter 1996-97 Messungen, die über sieben Monate hinweg in hohen Breiten aufgenommen wurden. Aufgrund der eingeführten Erweiterungen und Verbesserungen der Methode in dieser Arbeit, konnte die Methode anhand einer detaillierten Studie für den Winter 1996-97 validiert werden. Die ILAS Messreihe wurde dazu verwendet, erstmals die Untersuchung der zeitlichen Entwicklung von Ozon-Tracer Korrelationen kontinuierlich für die gesamte Lebensdauer des Polarwirbels durchzuführen. Dabei wurden auch Korrelationen während der Bildung des Wirbels untersucht und im Besonderen mögliche Mischungsvorgänge zwischen Wirbelluft und Luftmassen außerhalb des Wirbels. Ausserdem wurde ein Vergleich der Ergebnisse von ILAS und HALOE Messdaten durchgeführt und Unterschiede in den Ergebnissen tiefgreifend analysiert. Basierend auf HALOE Messungen konnte die erweiterte TRAC Methode über elf Jahren hinweg angewendet werden. Damit war erstmals eine konsistente Analyse von Ozonverlust und Chloraktivierung über diesen Zeitraum möglich. Die Erweiterungen führten zu einer Verringerung und genauen Quantifizierung von Unsicherheiten der Ergebnisse. Ein deutlicher Zusammenhang zwischen meteorologischen Bedingungen, Chloraktivierung und dem chemischen Ozonverlust wurde deutlich. Weiterhin zeigte sich eine Abhängigkeit zwischen den meteorologischen Bedingungen und der Homogenität des Ozonverlustes innerhalb eines Winters, sowie der mögliche Einfluss von horizontaler Mischung auf Luftmassen in einem schwach ausgeprägten Polarwirbel. In dieser Arbeit wurde eine positive Korrelation zwischen den über die gesamte Lebensdauer des Wirbels auftretenden möglichen PSC-Flächen und den akkumulierten Ozonverlusten für die elf untersuchten Jahre deutlich. Es konnte darüber hinaus gezeigt werden, dass der Ozonverlust von deutlich mehr Einflüssen als nur von der Fläche möglichen PSC Auftretens bestimmt wird, sondern zum Beispiel von der Stärke der Sonneneinstrahlung abhängt. Außerdem lassen sich Auswirkungen von Vulkanausbrüchen, wie zum Beispiel im Jahr 1991 der des Mount Pinatubo, identifizieren.
Barriereinseln und Außensände, geformt durch eine Kombination aus Wind, Wellen, Strömung und Küstenlängstransport gelten als morphologisch hoch aktive Küstenbereiche und variieren häufig in Ursprung, Genese und Entwicklung. Sie besitzen durch ihre dissipative Wirkungsweise eine bedeutende Schutzfunktion für rückwärtige Inseln, Halligen und Festlandbereiche und bilden vor der Küste Nordfrieslands die westliche Außengrenze des Wattenmeeres.
Ziel der nachfolgenden Studie ist es, anhand hochauflösender Georadarmessungen und sedimentologischer Daten aus Bohrungen die Landschaftsgeschichte an der Westküste Amrums sowie die Entstehung und interne sedimentäre Architektur des der Insel westlich angelagerten Kniepsandes zu untersuchen und die Prozesse, die zur Genese geführt haben, durch Datierungen zeitlich einzuordnen. Auf Grundlage der gewonnenen Daten wurden zwei stratigraphische Modelle entwickelt, welche die geologisch-geomorphologischen Prozesse und Sedimentationsbedingungen im Westküstenvorfeld erklären.
Ein Modell zeigt die Landschaftsentwicklung an der Westküste Amrums und beschreibt die Sedimentationsbedingungen, die im Vorfeld der Westküste herrschten, bevor der Kniepsand an die Insel heranwanderte. Auf der Landoberfläche des ertrinkenden saaleeiszeitlichen Geestkerns wurden zu Beginn der Flandrischen Transgression feinkörnige Sedimente eines Mischund Schlickwatts abgelagert. Es ist davon auszugehen, dass der damals noch weit vor der Küste Amrums liegende Kniepsand eine Barriere bildete und so an der heute hochenergetischen Westküste für strömungsberuhigte Sedimentationsbedingungen sorgte. Durch Erosion am Geestkern bildeten sich in unterschiedlichen Höhenpositionen fossile Kliffs, die dem damaligen Meeresspiegelstand entsprechen.
Ein weiteres Modell beschreibt den Andockmechanismus des Kniepsandes an die Insel Amrum. Durch die Anlagerung des ehemaligen Außensandes und den damit einhergehenden Sedimentinput wurden die Bedingungen für eine großflächige Dünenbildung geschaffen.
Barriereinseln und Nehrungshaken, geformt durch eine Kombination aus Wind, Wellen, Strömung und Küstenlängstransport gelten als geologisch junge und morphologisch hoch aktive Küstenbereiche und variieren häufig in Ursprung, Genese und Entwicklung. Bisherige Untersuchungen zur Stratigraphie dieser durch engräumige Fazieswechsel geprägten Sedimentationsräume basieren häufig allein auf Bohrungen. Daher sind die interne sedimentologische Struktur und die Prozesse, die zur Entwicklung von Barriereinseln und Nehrungshaken geführt haben, oftmals unzureichend untersucht.
Ziel der folgenden Studie war es, anhand hochauflösender Georadarmessungen (GPR) und Bohrungen die Entstehung und interne sedimentäre Architektur der Nehrungshaken von Sylt und Amrum zu rekonstruieren. Durch die Korrelation von Sediment- und Radarfazies konnten über den bisherigen Kenntnisstand hinaus wertvolle, sich ergänzende Informationen zur Geologie des oberflächennahen Untergrundes der Inseln Sylt und Amrum gewonnen werden. Auf dieser Grundlage wurden für den Süden Sylts, die Westküste von Amrum und den Norden Amrums stratigraphische Modelle entwickelt, die schematisch den sedimentologischen Aufbau, die geomorphologisch-geologische Genese und die am Aufbau beteiligten Prozesse zusammenfassen. Die Einordnung in einen absoluten Zeitrahmen wurde durch Datierungen (AMS Radiokohlenstoff-Methode, Aminosäure-Racemisierungs-Methode) ermöglicht.
Die Ergebnisse sind als Beispiel für die Heterogenität und Individualität von Nehrungshaken und Barriereinseln zu sehen. Es konnte gezeigt werden, dass Nehrungshaken hinsichtlich ihres Aufbaus, ihrer sedimentären Struktur sowie den Prozessen ihrer Entstehung sehr unterschiedlich sind.
Mit Ausnahme der heutigen Dünen zeigt die Stratigraphie der Ansatzzone des südlichen Nehrungshakens von Sylt an den zentralen Inselgeestkern südlich der Ortschaft Rantum insgesamt eine Vergröberungs-Sequenz von tonigem Mischwatt im Liegenden über Sandwatt bis zu den gröberen washover-Schichten im Hangenden. Eine Besonderheit und regionale Abweichung stellt die Stratigraphie bei Puan Klent/Thörnhörn dar. Dort wurde im Liegenden der Watt-Fazies ein fossiler Strandhaken nachgewiesen.
Die transgressive Sequenz der Ansatzzone des südlichen Nehrungshakens von Sylt bei Rantum auf Sylt ist kennzeichnend für eine landwärts gerichtete Wanderungsbewegung der Inselbarriere unter steigendem Meeresspiegel. Das Resultat des als „barrier rollover“ bezeichneten morphologischen Prozesses ist die allmähliche Erosion der westlichen Barrierefront. Das erodierte Sediment der Westküste wurde entweder durch overwash-Prozesse im rückwärtigen Inselbereich als washover fan abgelagert oder gelangte in den Küstenlängstransport, wurde zur Inselspitze transportiert und dort akkumuliert. Diese führte allmählich zum Wachstum und zur Progradation der südlichen Inselspitze (Hörnum Odde) in die sich südlich anschließende Tiderinne des Hörnum-Tiefs. Zahlreiche Erosionsdiskordanzen unterhalb des heutigen Meeresspiegels markieren ursprüngliche Inselspitzenendpositionen (time lines) und sind auf hochenergetische Sturmflutereignisse zurückzuführen. Die time lines werden nach Süden hin jünger und zeichnen unterschiedliche Stadien der Progradation nach, die ein episodisches Wachstum der Inselspitze in Abhängigkeit von der Sedimentverfügbarkeit und der Sturmflutintensität belegen. Alte Erosionsdiskordanzen belegen die frühe submarine Genese der Hörnum Odde. Ein starkes Wachstum der südlichen Inselspitze Sylts lässt sich im Mittelalter nachweisen.
Sturmfluten führten zudem immer wieder zu overwash-Prozessen und Überschwemmungen der noch jungen Inselspitze. Dies belegen ältere washover-Ablagerungen, die in unterschiedlichen Phasen der Nehrungshakenentwicklung nachgewiesen werden konnten. Rezente overwash-Prozesse sind auf die heutigen Dünen beschränkt und wurden in dieser Arbeit mit der Fragestellung untersucht, ob und inwieweit das Georadar als Methode zur Prospektion von washover-Sedimenten herangezogen werden kann.
Die unmittelbare Nachbarschaft der beiden Nehrungshaken von Sylt und Amrum lässt einen ähnlichen sedimentären Aufbau, eine analoge Genese in einem einheitlichen Prozess-System sowie ein vergleichbares Alter vermuten. Durch die Untersuchungen im Norden von Amrum sollte festgestellt werden, in wie weit das für die Hörnum Odde nachgewiesene Zusammenspiel von Küstenlängstransport, Progradation, sturmflutbedingten overwash-Prozessen und die zeitliche Unterbrechung des Längenwachstums durch Sturmfluterosion auch für Amrum zutrifft. Entgegen der Erwartungen unterscheidet sich der nördliche Nehrungshaken der Insel Amrum signifikant vom südlichen Nehrungshaken der Nachbarinsel Sylt.
Studien zur Landschaftsentwicklung an der Westküste Amrums wurden in einem Modell zusammengefasst, dass die Sedimentationsbedingungen, die im Westküstenvorfeld herrschten bevor der Kniepsand an die Insel heranwanderte, beschreibt. Auf der Landoberfläche des ertrinkenden saaleeiszeitlichen Geestkerns wurden zu Beginn der Flandrischen Transgression feinkörnige Sedimente eines Misch- und Schlickwatts abgelagert. Es ist davon auszugehen, dass der damals noch weit vor der Küste Amrums liegende Kniepsand eine Barriere bildete und so an der heute hochenergetischen Westküste für strömungsberuhigte Sedimentationsbedingungen sorgte. Ein weiteres Modell beschreibt den Andockmechanismus des Kniepsandes an die Insel Amrum. Durch die Anlagerung des ehemaligen Außensandes und den damit einhergehenden Sedimentinput wurden die Bedingungen für eine großflächige Dünenbildung geschaffen.
Die vorliegende Arbeit stellt einen Ansatz zur Systematisierung der Konzeption und Entwicklung webbasierter multimedialer Lehr-/Lernobjekte (mmL-Objekte) in der Physischen Geographie, im Wesentlichen in der Teildisziplin Geomorphologie, vor. Auf allgemeine Ausführungen zu mediendidaktischen Grundlagen und Begrifflichkeiten im Zusammenhang internetgestützter Lehr-/Lernszenarien folgt die Darstellung von Strategien der Wissensstrukturierung, Wissensaneignung und fachwissenschaftlicher Methodik im Lehr-/Lernkontext geomorphologischer Prozesse und ihrer Modellierung im Internet. Die Aufbereitung des Prozesskomplexes Bodenerosion seht im Mittelpunkt. Ein Überblick über Potentiale computergestützter Modellierung und Visualisierung zur Entwicklung webbasierter multimedialer Lehr-/Lernmaterialien in der Geographie leitet über zur Erarbeitung eines präskriptiven Ansatzes zur Konzeption interaktiver Lernaufgaben. Sie setzen sich zusammen aus einer Visualisierungskomponente, den Möglichkeiten zur Interaktion mit der Visualisierung und mindestens einer Aufgabenstellung. Vor allem in computerunterstützten Lehr-/Lernprozessen, die selbständiges Lernen erfordern, erweisen sie sich als wesentliches didaktisches Element, um sicherzustellen, dass sich Lernende aktiv und nicht nur rezeptiv mit Inhalten und Medien in der für erfolgreiche Lernprozesse erforderlichen Intensität auseinander setzen. Ausgehend von der Funktion des zu entwickelnden Lehr-/Lernangebotes und dem jeweiligen angestrebten Zielhorizont eines Lehr-/Lernelements werden Empfehlungen zur Konstruktion aufgabenorientierter mmL-Objekte vorgeschlagen. Exemplarisch wird die praktische Anwendung theoretisch begründeter Empfehlungen anhand von aufgabenorientierten mmL-Objekten (interaktiven Lernaufgaben) aufgezeigt und diskutiert, die im Rahmen des BMBF-Projektes „WEBGEO – Webbing von Geoprozessen für die Grundausbildung Physische Geographie“ und im Rahmen der Lehrveranstaltung „Erstellung von E-Learning-Modulen durch Studierende“ entwickelt wurden.
This study presents a comprehensive and critical assessment of the meteorological conditions and atmospheric flow during the Lagrangian-type "Hill Cap Cloud Thuringia 2010" experiment (HCCT-2010). HCCT-2010 was performed in September and October 2010 at Mt. Schmücke in the Thuringian forest, Germany, applying three measurements sites (upwind, in-cloud, downwind) to study physical and chemical aerosol-cloud-interactions. A Lagrangian-type hill cap cloud experiment requires suitable cloud and particularly connected airflow conditions, i.e. representative air masses at the different measurement sites. Therefore, the present study aimed at the identification of time periods during the 6-weeks duration of the campaign, where such conditions were fulfilled and which can be used in further data examinations.
The following topics were studied in detail: (i) the general synoptic weather situations including the mesoscale flow conditions by means of a classification of advected air masses and calculation of non-dimensional flow parameters (e.g. Froude number), (ii) local meteorological conditions, including synoptic front passages, the presence of orographic or frontal cloudiness, cloud base heights and vertical stratification, and (iii) local flow conditions by means of statistical analyses using the quasi-inert trace gas ozone and selected size bins of particle number size distributions as well as SF6 tracer experiments in the campaign area. A comprehensive analyses using statistical measures such as the COD (Coefficient Of Divergence) and cross-correlation have been carried out for the first time in the context of a Lagrangian-type hill cap cloud experiment. Suitable criteria for the aimed statistical analyses were thus developed and applied in the present study to characterise the local flow connectivity in detail.
The comprehensive examination resulted in a total of 14 so-called "Full Cloud Events" (FCE), which are shown to conform to the Lagrange-type experimental philosophy of HCCT-2010. In addition, 15 so-called "Non-Cloud Events" (NCEs) could be established, which can be used as reference cases as they provide similarly suitable flow conditions but no cloud at the summit site. Orographic cloudiness was identified for approx. one third of the FCE periods, while about two thirds were associated to synoptic fronts. The statistical flow analyses indicate the existence of a strong link between the sites during the events, particularly under constant south-westerly flow conditions, high wind speeds and slightly stable stratification. The COD analyses using continuously measured concentrations of ozone and the 49 nm diameter particle bin revealed particularly for COD values below 0.1 very consistent time series, i.e. closely linked air masses between the different sites. The cross-correlation analysis revealed under connected flow conditions typical overflow times of about 15 to 30 min between the two valley sites. Additionally, the performed SF6 tracer experiments during the campaign clearly demonstrate that under appropriate meteorological conditions a Lagrangian-type approach is valid and that the connected flow validation procedure developed in this work is suitable for identifying such conditions. Finally, an overall evaluation of the identified FCEs is presented, which provides the basis for subsequent investigations of the measured chemical and physical data during HCCT-2010.
The Altenberg–Teplice Volcanic Complex (ATVC) is a large ~ NNW–SSE trending volcano-plutonic system in the southern part of the Eastern Erzgebirge (northern Bohemian Massif, south-eastern Germany and northern Czech Republic). This study presents high precision U–Pb CA-ID-TIMS zircon ages for the pre-caldera volcano-sedimentary Schönfeld–Altenberg Complex and various rocks of the caldera stage: the Teplice rhyolite, the microgranite ring dyke, and the Sayda-Berggießhübel dyke swarm. These data revealed a prolonged time gap of ca. 7–8 Myr between the pre-caldera stage (Schönfeld–Altenberg Complex) and the climactic caldera stage. The volcanic rocks of the Schönfeld–Altenberg Complex represent the earliest volcanic activity in the Erzgebirge and central Europe at ca. 322 Ma. The subsequent Teplice rhyolite was formed during a relatively short time interval of only 1–2 Myr (314–313 Ma). During the same time interval (314–313 Ma), the microgranite ring dyke intruded at the rim of the caldera structure. In addition, one dyke of the Sayda-Berggiesshübel dyke swarm was dated at ca. 314 Ma, while another yielded a younger age (ca. 311 Ma). These data confirm the close genetic and temporal relationship of the Teplice rhyolite, the microgranite ring dyke, and (at least part of) the Sayda-Berggießhübel dyke swarm. Remarkably, the caldera formation in the south of the Eastern Erzgebirge (caldera stage of ATVC: 314–313 Ma) and that in the north (Tharandt Forest caldera: 314–312 Ma) occurred during the same time. These data document a large ~ 60 km NNW–SSE trending magmatic system in the whole Eastern Erzgebirge. For the first time, Hf-O-isotope zircon data was acquired on the ring dyke from the ATVC rocks to better characterize its possible sources. The homogeneous Hf-O-isotope zircon data from the microgranite ring dyke require preceding homogenization of basement rocks. Some small-scale melts that were produced during Variscan amphibolite-facies metamorphism show similar Hf-O-isotope characteristics and can therefore be considered as the most probable source for the microgranite ring dyke melt. In addition, a second source with low oxygen isotope ratios (e.g. basic rocks) probably contributed to the melt and possibly triggered the climactic eruption of the Teplice rhyolite as well as the crystal-rich intrusion of the ring dyke.