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The present PhD-thesis was prepared within subproject B8 of the DFG-Sonderforschungsbereich (SFB) 641 “The Tropospheric Ice Phase”. The subproject B8 was entitled “Interactions of volatile organic compounds with airborne ice crystals”. Results of previous studies have shown that various volatile organic compounds (VOC) and semivolatile organic compounds (SVOC) are incorporated into the atmospheric ice phase and several uptake mechanisms are discussed in the literature. The aim of this study was to identify the dominating VOC and SVOC in airborne snow collected at Jungfraujoch in the Swiss Alps (3580 m asl) and to study in laboratory experiments the uptake mechanism of organic compounds into snow and ice. For this purpose an analytical method to analyse freshly fallen snow samples was developed and evaluated in a first step. The method consists of headspace (HS) solid phase dynamic extraction (SPDE) followed by gas chromatography combined with mass spectrometry (GC/MS). During the extraction process a new cooling device was successfully integrated into the HS-SPDE-GC/MS method to enhance the extraction yield. Extraction and desorption parameters such as the number of extraction cycles, extraction temperature, desorption volume and desorption flow rate have been optimized. Detection limits for benzene, toluene, ethylbenzene, m-, p-, o- xylene (BTEX) ranged from 19 ng L-1 (benzene) to 30 ng L-1 (m/p-xylene), while those for C6-C10 n-aldehydes ranged from 21 ng L-1 (n-heptanal) to 63 ng L-1 (n-hexanal). Furthermore, freshly fallen snow samples were collected at the High Altitude Research Station Jungfraujoch (3580 m asl, Switzerland) during the field campaigns “Cloud and aerosol characterization experiment” (CLACE) 4 and 5 in February and March 2005 and 2006, respectively. Freshly fallen snow samples collected directly in-cloud on a high altitude remote location were used as approximation of airborne ice crystals since sampling of airborne ice crystals in quantities sufficient for analysis of individual organic compounds is not yet possible. In the collected snow samples a wide range of organic compounds were identified, namely BTEX, n-aldehydes (C6-C10), terpenes, chlorinated hydrocarbons and alkylated monoaromatics. The most abundant organic compounds in snow samples from Jungfaujoch during CLACE 4 and 5 were n-hexanal with a median concentration of 1.324 μg L-1 (CLACE 5) followed by n-nonanal (CLACE 5) with a median concentration of 1.239 μg L-1. High concentration variations of the analytes in snow samples collected at the same time at the same place argue for a heterogeneous composition of snow and ice. Several indicators were found that the origin of the n-aldehydes in the snow can be attributed to direct biogenic emissions from vegetation and indirect biogenic emissions through photochemical oxidation of fatty acids and alkenes. In a second step laboratory experiments were carried out to clarify the uptake mechanism of volatile and semivolatile organic compounds into snow/ice. Organic compounds can be incorporated into the atmospheric ice phase either by the process of gas scavenging, liquid scavenging (riming) or particle scavenging. Gas scavenging (incorporation of the organic compounds from the gas phase during growing of ice crystals) revealed to be ineffective based on previous laboratory experiments in which ice crystals were growing in the presence of aromatic hydrocarbons (BTEX) in the gas phase. In the present study the process of liquid scavenging (riming) was investigated in the laboratory using aqueous standard solutions containing BTEX, naldehydes (C6-C10), methyl tert-butyl ether (MTBE) and ethyl tert-butyl ether (ETBE). The headspace above the standard solution was sampled after adjusting the aqueous solutions to definite temperatures by use of a thermostat. Measurement were carried out at 25°C, 15°C and 5°C (water), -5°C and -15°C (supercooled water) and -25°C (ice). Results have shown that the known trend of lower gas phase concentrations over water concomitant with lower temperatures (Henry’s Law) is only valid for temperatures above 0°C. At temperature below 0°C, increasing concentrations of the analytes (BTEX, MTBE, ETBE and n-aldehydes) were determined in the gas phase together with decreasing temperatures. Dimensionless Henry’s law coefficients (KAW) were calculated from the concentrations of the organic compounds in the headspace above the standard solutions at temperatures between 25°C and -25°C. The observed inversion of Henry’s law coefficients of volatile and semivolatile organic compounds at a water temperature of approximately 0°C is explained by the formation of ordered zones of H2O molecules in supercooled water called “ice-like-clusters”. Together with decreasing temperatures the degree of formation of ordered zones increases which results in the removal of the organic molecules from the liquid phase and transfer into the gas phase. At a temperature of -25°C the supercooled water is converted into ice and a further significant increase of the gas phase concentrations of hydrophobic compounds such as BTEX is observed. In comparison, less hydrophobic compounds such as MTBE, ETBE and n-aldehydes are detected in lower amounts in the gas phase above the water/ice phase due to the higher water solubility and lower Henry coefficients compared to BTEX. The results show that in the absence of particles the uptake of BTEX MTBE, ETBE and C6-C10-naldehydes into ice not enhanced during freezing of a supercooled liquid, since at -25°C for these analytes the concentrations in the gas phase are higher at -25°C (ice) compared with -15°C (supercooled liquid). The heterogeneous distribution of BTEX and n-aldehydes concentrations in snow samples collected during the CLACE field campaigns suggests that adsorption of the organic compounds to particles followed by incorporation of the particles into the snow and ice might play a major role in the uptake process of organic compounds into snow and ice. To increase the knowledge about uptake processes of organic compounds into snow and ice further experiments are required with should include aerosol particles in the experimental setup to evaluate the influence of particle scavenging in the uptake processes.
Delthyridoid spiriferids are characterized by a global abundance and fast evolution during Silurian and Devonian, and, therefore, are used as important biostratigraphical and palaeobiogeographical tools. In this work, delthyridoid brachiopod faunas from different regions of today’s world, resp., of different palaeobiogeographical units, are compared side-by-side to investigate their phylogenetic relationships and to improve, in a second step, the palaeobiogeography from Late Silurian to Early Eifelian time. A new systematics of Delthyridoidae is established which is more complicated than hitherto assumed. The results of this study are mainly based on direct comparison of articulated and isolated brachiopod shells, external and internal moulds, as well as latex casts and serial sections. The computer supported cladistic analyses have turned out not to be useful due to different kinds of preservation resulting in an incomplete matrix which is insufficient for reliable cladograms. A further problem in terms of cladistical analyses are various convergences during the evolution of spiriferids. Many characters evolved independently from each other at different times in each lineage so that autapomorphies are hardly or not at all recognizable. As a result, families and genera are only definable by a combination of characters rather than by a single or a few autapomorphies. As a new method, 3D reconstruction from serial sections is introduced which made it possible for the first time to compare directly mouldic and shelly material. Preliminary results are presented herein. Statistical analyses of measurements taken from new taxa are made but regarded as a descriptive argument rather than a deciding factor for taxonmy due to incomplete preservation and/or tectonic deformation. Brachiopods, especially type material, from collections of different institutions and museums are studied as well as personal material, whenever possible collected from topotype outcrops. Emended diagnoses, if necessary, from family to species level are given. During this work several new taxa have been erected: 7 new families: Australospiriferidae, Murchisonispiriferidae, Orientospiriferidae, Otospiriferidae, Patriaspiriferidae, Rostrospiriferidae, and Trigonospiriferidae; 6 new genera, 1 of these in open nomenclature: Cyclopterospirifer, Hallispirifer, Parlinispirifer, Murchisonispirifer, Shujiapingensispirifer, and gen. nov. B; and 3 new species: Patriaspirifer merriami, Patriaspirifer johnsoni, and Murchisonispirifer feldmani; 1 taxon is defined as nomen novum: Orientospirifer nakaolingensis wani. In the framework of this project, 2 families: Filispiriferidae and Multispiriferidae; 1 subfamily: Multiplicatispiriferinae, 6 genera, 1 of them in open nomenclature: Frequentispirifer, Leonispirifer, Multiplicatispirifer, Ovetensispirifer, Turcispirifer, and Gen. A; and 9 new species, 3 of them in open nomenclature: Filispirifer hamadae, Leonispirifer leonensis, Multiplicatispirifer foumzguidensis, Oventensispirifer novascotianus, Quiringites arensentiae, Turcispirifer turciae, Multiplicatispirifer cf. foumzguidensis, Quiringites cf. arensentiae, and ?Turcispirifer sp. A which have already been established are also described in this work. The brachiopod faunas studied consist of externally very similar spiriferids which have been identified as same genera, species, or even subspecies in earlier times. These forms are considered as 6 distinct morphotypes Howellella-, Arduspirifer-, Acrospirifer-, Euryspirifer-, Paraspirifer-, and Multiplicatispirifer-like morphotypes, which are briefly introduced. The new systematics is characterized by different clades, the European/North African delthyridoid spiriferid clade, the North American delthyridoid spiriferid clade, the Asian delthyridoid spiriferid clade, the Malvinokaffric delthyridoid spiriferid clade, and the delthyridoid multiplicated spiriferid clade. Each of them is described in a cladistic and in a phylogenetic way. Their phylogenetic relationship sheds new light on palaeobiogeographical interpretations for the different stages from Late Silurian to early Middle Devonian time. A tendency for increasing endemicity is seen until the end of the Early Emsian, which is interrupted by short term regional faunal exchange within a province or within a realm, followed by a loss of endemicity resulting in global distribution of brachiopod genera until the end of Givetian time. The Old World Realm is re-defined due to the lack of phylogenetic relationship between its faunas and subdivided into the European Realm, consisting of the Gondwanan and Avalonian provinces, and the Asian Realm, consisting of the Siberian, Sino, and Mongolian provinces. A reconstruction of Lower Devonian palaeobiographical map is introduced.
NASAs Stardust Mission ist die erste Mission, die - nach den Apollo Missionen zum Mond - Material von einem extraterrestrischen Körper erfolgreich für die Untersuchung auf der Erde, zurückgebracht hat. Desweiteren konnten erfolgreich Proben von einem Interstellaren Partikelstrom aufgesammelt werden, der das Sonnensystem derzeit passiert. Die Mission erlaubt einen Einblick in die Beschaffenheit der Kometenpartikel, die Rolle von Kometen im Sonnensystem sowie den Eintrag von Staub in die Zodiakalwolke. Desweiteren erlaubt die Analyse der Kometenpartikel den direkten Vergleich zu bereits untersuchten Meteoriten und Interplanetaren Staub Partikeln (IDPs) die auf der Erde bzw. deren Stratosphäre gesammelt wurden. Stardust ist die vierte ”Discovery” Mission und wurde am 7. Februar 1999 gestartet. Während des Fluges zum Kometen 81P/Wild 2 wurde ein interstellarer Partikelstrom beprobt und der Asteroid Annefrank passiert. Nach fünf Jahren kam es zum Zusammentreffen mit dem Kometen 81P/Wild 2 und über fünf Minuten, wurden Proben mit einer Auffangvorrichtung eingesammelt. Es dauerte weitere zwei Jahre bis die Stardust Sonde die Proben erfolgreich zur Erde zurückgebracht hat und zur Untersuchung freigegeben wurden. Interstellare und kometare Partikel wurden mit einer tennisschlägerartigen Auffangvorrichtung eingefangen, die aus einer Vielzahl von Aerogel Zellen aufgebaut ist. Das für die Stardust Mission verwendete Aerogel besteht aus SiO2 dessen dendritische Struktur zu 99,8 % aus Luft (Poren) besteht. Dadurch erscheint es nahezu transparent, was die optische Suche mit Mikroskopen nach den Einschlagsspuren der Körner vereinfacht. Die jeweiligen Partikel wurden auf unterschiedlichen Seiten der Vorrichtung eingefangen, da unterschiedliche Eigenschaften des Aerogels notwendig waren und um sie später voneinander unterscheiden zu können. Die Seite, in der die Kometenpartikel eingefangen wurde, musste Körner mit unterschiedlichen Grössen, Morphologien und niedrigeren Geschwindigkeiten abbremsen, während auf der interstellaren Seite die Körner von wesentlich höheren Geschwindigkeiten abgebremst werden mussten. Die Aerogelzellen haben ein variierendes Dichteprofil: an der Oberfläche ist die Dichte geringer (5 mg/ml) und erhöht sich mit der Tiefe auf 30-50 mg/ml. Dieses Dichteprofil ist notwendig, da beim Einschlag der Körner auf das Auffangmedium ein hoher Druck entsteht, der umso geringer ist, je niedriger die Dichte im Moment des Auftreffens ist. Die Aerogelzellen für die Kometenpartikel haben drei Lagen mit unterschiedlichen Dichten, die Zellen für die interstellaren Körner haben zwei unterschiedliche Dichten (Tsou et al., 2003)....
New industries are recognized as new impetus to national wealth. At the same time, they are increasingly becoming geographically concentrated in some well defined areas. But current studies on the emergence of industrial clusters tend to analyze favorable driving factors. This dissertation takes the example of a Chinese endogenous industrial cluster, the traditional Chinese medicine (TCM) cluster at Tonghua, a small peripheral city in Northeastern China, to contribute to the theoretical understanding of the emergence of industrial cluster as a co-evolutionary process of organizations, institutions and firms, or, to put it more broadly, as economic evolution embedded in complex socio-economic contexts. The recent advance in evolutionary and co-evolutionary economics which considers the economy and economic landscape as dynamic process instead of equilibrium can be regarded as a part of broader and more intellectual turn of quest for history in social sciences. Although the principle of "history matters" is widely acknowledged, it tends to be reduced to a quite simple concept of "path dependence". However, path dependence cannot offer space for new path creation, except from an external shock. Accordingly, the role of human conscious action or Schumpeterian innovation should be added to path analysis through the concept of path creation. Furthermore, and more importantly, history should be understood as context, and historical context can be explored through the understanding of multi-paths and interaction among them over time. So path inter-dependence (co-evolution between paths) would be useful to better understand the complexity of real history. Since the industrial cluster is composed of interconnected firms and is also subject to changes in institution and technology, I will focus on the multi-way causal relationship between firm, institution and technology. The theorizing is not entirely new, but most of the theoretical and empirical discussions are at the national or industrial level, not regional or local one. A competitive cluster can be regarded as a co-evolutionary hotspot in which multiple populations actively interact and are interconnected. Co-evolution itself is a dynamic and evolutionary process. So I will adopt a dynamic and evolutionary view to examine co-evolutionary degree or co-evolutionary effects in the Tonghua pharmaceutical cluster through time. After a brief introduction which deals with the national institutional changes that are highly associated with new venture creation, entrepreneurship, and innovation, with registrations on drug and healthcare system, and with changes in market demand of China’s pharmaceutical industry and geographical distribution, I will collect evidences from three aspects based upon field survey and second hand data, i.e., the history of the enterprises, the origin of entrepreneurship, and the knowledge of evolution, linking their respective generative relationships through the genealogical method. In this volume, the evolution of the Tonghua pharmaceutical firm organization, the formation of local entrepreneurship, historical accumulation of knowledge, and particular knowledge of transfer among generations of firms will be discussed, then I will probe into co-adaption and co-evolution between local formal and informal institutions and organizations in Tonghua’s TCM industry. In addition, I will try to understand the co-evolutionary process at different geographical levels (namely, national and local). In summary, my main findings include the following several points. Firstly, in the course of the emergence of Tonghua’s pharmaceutical industry, local social networks and the traditional alliance between enterprises and government have played important roles. Secondly, the most important factor that influences the evolution of endogenous industrial clusters such as the Tonghua pharmaceutical industry in transitional countries is not the change in technology, but the change in fundamental national institutions. Thirdly, the success of the Tonghua pharmaceutical industry can be ascribed to the creation of multiple paths largely based on initial conditions, which implies that economic policy should have historical consciousness, namely, new economic innovation should make full use of both historical legacies and existing assets. Finally, it is co-adaption and co-selection of firm organization, institution, and technology that have jointly made Tonghua’s pharmaceutical industry become highly competitive, which means that whether one region can grasp new opportunities partially depends on its capabilities to coordinate a varity of development agents.
Trace elemental concentrations of bivalve shells content a wealthy of environmental and climatic information of the past, and therefore the studies of trace elemental distributions in bivalve shells gained increasing interest lately. However, after more than half century of research, most of the trace elemental variations are still not well understood and trace elemental proxies are far from being routinely applicable. This dissertation focuses on a better understanding of the trace elemental chemistry of Arctica islandica shells from Iceland, and paving the way for the application of the trace elemental proxies to reconstruct the environmental and climatic changes. Traits of trace elemental concentrations on A. islandica shells were explored and evaluated. Then based the geochemical traits of the shells, four non-environmental/climatic controlling is indentified. (1) Trace elemental concentrations of bivalve shells are effected by early diagenesis by the leach or exchange of elemental ions, especially in shell tip part, even with the protection of periostrucum; (2) The analytical methods also affect the results of trace elemental concentrations, especially for the element, such as Mg, which is highly enriched in organic matrices; (3) Shell organic matrices are found play a dominating role on the concentration of trace elements on A. islandica shells. Most trace elements only occurred in insoluble organic matrices (IOM), although others are only found in the carbonate fraction. IOM of A. islandica shells is significantly enriched in Mg, while Li and Na are more deplete in IOM, but enriched in shell carbonate. Ba is more or less even contented in IOM and shell carbonate. The concentrations of certain elements vary between primary layer and secondary layer; (4) The vital /physiological controlling on trace elemental distributions of bivalve shells is also confirmed. Six elemental (B, Na, Mg, Mn, Sr, and Ba) concentrations show significant correlation (exponential functions) with ontogenetic age and shell grow rates (logarithmic equations). It is worthy to remark that B, Mg, Sr and Ba concentrations are negatively correlated with shell growth rate, positive with ontogenetic age, while the concentrations of Na and Mn show the opposite trends. At last, all the controlling described above can be taken into account and corrected to extract the environmental and climatic signal by a kind of standardization. The derived six exponential functions of the high correlations between six trace elemental concentrations and ontogenetic year are applied to make the standardization of these element-Ca ratios. The gotten standardized indices are compared with the variations of environmental and climatic parameters in this region, and many correlations are found. Standardized indices of Sr/Ca ratios are strongly related to the sun spot number, autumn NAO, autumn Europe surface air temperature (SAT) and Arctic sea surface temperature anomaly (TA), and those of Mg/Ca ratios are strongly associated with Arctic TA, Europe SAT and Solar variation (irradiance). The variations of autumn Europe SAT demonstrated more similarity with standardized indices of B/Ca than other parameters. Except for the SAT index of Arctic, the standardized indices of Na/Ca showed no distinct relation to temperature. European precipitation and the Arctic sea level pressure index compared well the Na/Ca ratios of the shells, and so did the autumn NAO. Standardized indices of Mn/Ca were correlated with the number of hurricanes in the North Atlantic, Northern Europe SAT and sun spot number.
The crude oil constituents benzene, toluene, ethylbenzene, and the three xylene isomers (BTEX) are the dominating groundwater contaminants originating from surface spill accidents by oil production facilities and with gasoline and jet fuel. Thereby BTEX posing a threat to the world´s scarce drinking water resources due to their water solubility and toxicity. An active remediation cleanup involving a BTEX event proves not only to be very expensive but almost impossible when it comes to the complete removal of contaminants from the subsurface. A favoured and common practice is combining an active remediation process focussing on the source of contamination coupled together with the monitoring of the residual contamination in the subsurface (monitored natural attenuation; MNA). MNA include all naturally occuring biological, chemical and physical processes in the subsurface. The general goal of this work was to improve the knowledge of biodegradation of aromatic hydrocarbons under anaerobic conditions in groundwater. For this groundwater and soil at the former military underground storage tank (UST) site Schäferhof – Süd near Nienburg/Weser (Niedersachsen, Germany) were sampled and analysed. The investigations were done in collaboration of the Umweltbundesamt, the universitys of Frankfurt and Bremen and the alphacon GmbH Ganderkesee. To investigate the extent of groundwater contamination, the terminal electron acceptor processes (TEAPs) and the metabolites of BTEX degradation in groundwater, six observation wells were sampled at regular intervals between January 2002 and September 2004. The wells were positioned in order to cover the upstream, the source area and the downstream of the presumed contamination source. Additionally, vertical sediment profiles were sampled and investigated with respect to spreading and concentration of BTEX in the subsurface. A large residual contamination involving BTEX is present in soil and groundwater at the studied locality. Maximum BTEX concentration values of 17 mg/kg were recorded in analysing sediment in the unsaturated zone. In the capillary fringe, values of 450 mg/kg were recorded (October 2004) and in the saturated zone maximum values of 6.7 mg/kg BTEX were detected. The groundwater samples indicate increasing BTEX concentrations in the groundwater flow direction (from 532 µg/l up to 3300 µg/l (mean values)). Biodegradation of aromatic hydrocarbons under anaerobic conditions in the sub surface at contaminated sites is characterised by generation of metabolites. From the monoaromatic hydrocarbons BTEX metabolites such as benzoic acid (BA) and the methylated homologs and C1-and C2-benzyl-succinic acids (BSA) are generated as intermediates. A solid-phase extraction method based on octadecyl-bonded silica sorbent has been developed to concentrate such metabolite compounds from water samples followed by derivatization and gas chromatography/mass spectrometry (GC/MS) of the extracts. The recovery rate range between 75 and 97%. The method detection limit was 0.8 µg/l. Organic acids were identified as metabolic by-products of biodegradation. Benzoic acid, C1-, C2- and C3-benzoic acid were determined in all contaminated wells with considerable concentrations. Furthermore, the depletion of the dominant terminal electron acceptors (TEAs) oxygen, nitrate, and sulphate and the production of dissolved ferrous iron and methane in groundwater indicate biological mediated processes in the plume evidently proving the occurrence of NA. A large overlap of different redox zones at the studied part of the plume has been observed. A important finding in this study is the strong influence of groundwater level fluctuations on the BTEX concentration in groundwater. A very dry summer in 2003 was recorded during the monitoring period, resulting on site in a drop of the groundwater level to 1.7 m and a concomitant increase of BTEX concentrations from 240 µg/l to 1300 µg/l. The groundwater level fluctuations, natural degradation and retention processes essentially influence BTEX concentrations in the groundwater. Groundwater level fluctuations have by far a stronger influence than the influence of biological degradation. Increasing BTEX concentrations are hence not a consequence of limited biological degradation. Another part of the study was to observe the isotopic fractionation of the electron acceptor Fe(III), due to biologically mediated reduction of Fe(III) to the watersoluble Fe(II) at the site and first field data are presented. Both groundwater and sediment samples were analysed with respect to their Fe isotopic compositions using high mass resolution Multi Collector-Inductively Coupled Plasma-Mass Spectrometry (MC-ICP-MS). The delta56Fe -values of groundwater samples taken from observation wells located downstream of the source area were isotopically lighter than delta56Fe -values obtained from groundwater in the uncontaminated well. The Fe isotopic composition of most parts of the sediment profile was similar to the Fe isotopic composition of uncontaminated groundwater. Thus, a significant iron isotope fractionation can be observed between sediment and groundwater downstream of the BTEX contamination.
Die vorliegende Arbeit beschäftigt sich mit der geochemischen und isotopischen Analyse detritischer Zirkonminerale aus rezenten Sedimenten des weit verzweigten Orange- und Vaal River Flusssystems in Südafrika. Zirkone kristallisieren überwiegend aus krustalen Schmelzen und sind äußerst resistent gegenüber jeglicher Zerstörung und damit ein idealer Kandidat zur Rekonstruktion früherer Krustenbildungsprozesse der geologischen Erdgeschichte. Der kombinierte Ansatz der U-Pb Altersdatierung, der Hf Isotopie und der Spurenelementgeochemie mittels Laserablation und des Einsatzes induktiv-gekoppelter Sektorfeld- und Multikollektormassenspektrometer ermöglicht es die krustale Wachstums- und Entwicklungsgeschichte des südafrikanischen Kratons zu erfassen. Die mehr als 1200 U-Pb Analysen der Zirkone weisen 4 tektonische Hauptphasen des südafrikanischen Kontinents nach: 1. die Panafrikanische Orogenese (0.5-0.7 Ga), 2. das Namaqua-Natal Faltengürtelorogen (1.0-1.3 Ga), 3. die Kheis Orogenese (1.8-2.0 Ga) und 4. die westliche Kaapvaal-Kratonisierung (2.9-3.2 Ga). Allerdings zeigt sich, dass die 13 Probenlokationen überwiegend lokale bzw. regionale U-Pb Altersdaten ihrer umgebenden Herkunftsgebiete liefern. Die Hf Isotopie der Zirkone der verschiedenen tektonischen Hauptphasen Südafrikas stellen ihre differenzierte Akkretions- und Aufschmelzungsgeschichte dar. Die panafrikanischen Zirkone zeigen eine ausgeprägte Durchmischung von juvenilem und recyceltem Material. Die mesoproterozoischen (Namaquan) Zirkone entstanden aus juvenilem Magma während eines Inselbogen-Kontinent-Kollisionsereignisses. Die paläoproterozoischen und archaischen Zirkone sind Produkte von aufgeschmolzener prä-existierender kontinentaler Kruste oder vom Mantel abstammende Schmelzen, die durch kontinentale Kruste kontaminiert wurden. Die berechneten Hf Modellalter, so genannte „Mantelextraktionsalter" ergeben zwei Maxima, die zwei Stadien juvenilem Krustenwachstums einschließen, einmal vor 1.4 und 3.2 Ga. Dieses krustale Wachstum zeigt eine Übereinstimmung mit den progressiv episodischen Modellen von Nagler & Kramers (1998) sowie Condie (2000) mit Höhepunkten zwischen 3.0 und 2.0 Ga sowie den Studien von Wang et al. (2008) mit krustalen Wachstumsperioden von 1.6 bis 2.2 und 2.9 bis 3.4 Ga auf dem Nordamerikanischen Kontinent und auf dem Gondwana-Kontinent (Australien) von Hawkesworth & Kemp 2006) und implizieren wohl ein globales kontinentales Krustenwachstum. Die Abgrenzung und Wiedererkennung der Zirkone anhand der chemischen Zusammensetzung zu möglichen Muttergesteinen zeigen noch keine viel versprechenden Ergebnisse. Generell weisen die Zirkone eine magmatische granitoide Zusammensetzung kontinentalen Ursprungs auf. Eine Auffälligkeit stellen die erhöhten Spuren- und leichten Seltenenerdelemente in Zirkonen jeglicher Altersklassen dar. Nachfolgende Arbeiten müssen zeigen, wie und ob diese Anreicherungen Einfluss auf die chemische Zusammensetzung, die U-Pb Datierung und vor allem die Hf-Isotopie der Zirkone haben.
Der neoproterozoische Faltengürtel Kameruns (NFBC) ist durch Zahlreiche Pan- Afrikanische Plutone charakterisiert, die von krustalen Scherzonen durchsetzt werden. Der NFBC resultiert aus der Konvergenz des Westafrikanischen und des Kongo/Saõ-Francisco Kratons. Die Borborema Provinz (BOP) in NE-Brasilien wird als Äquivalent des NFBC angesehen. Bisher vorliegende Daten legen nahe dass die Borborema Scherzonen in kontinentaler Kruste durch dextrale Extrusion der BOP enstanden sind. Letztere wurde durch differentielle Bewegungen (Rotation induziert durch Subduktion und Kollision) des Kongo/Saõ- Francisco und des Westafrika-Kratons ausgelöst. Die Aktivität der Scherzonen fällt mit einer Hochtemperatur-Mittel- bis Niederdruckmetamorphose zusammen, welche mit partieller Aufschmelzung und Intrusion krustaler sowie Mantelschmelzen einhergeht. Die Bewegungen entlang dieser Scherzonen begannen zwischen 590 und 570 Ma und hielten bei abnehmender Temperatur bis etwa 500 Ma an. Ob die Scherzonen der BOP tatsächlich in den NFBC hineinreichen, war bisher nicht eindeutig geklärt. Die tektonometamorphe und magmatische Entwicklung des NFBC ist aufgrund fehlender struktureller, petrologischer und geochronologischer Daten kaum verstanden. Die vorliegende Arbeit befasst sich mit der Platznahme und Deformation der Plutone im Bereich des westlichen NFBC in der Region von Bafoussam-Batcha. Es wurden strukturelle Untersuchungen sowie U-(Th)-Pb Datierungen von Zirkon und Monazit durchgeführt. Die gewonnenen Daten werden mit bisher vorliegenden Daten aus den benachbarten Arealen des NFBC und aus äquivalenten Arealen Brasiliens verglichen. Innerhalb des NFBC lassen sich drei wesentliche proterozoische Gesteinseinheiten unterscheiden: (1) hoch-gradige metamorphe Komplexe mit palaeoproterozoischem Alter (Eburnium), bestehend aus Metasedimenten und Metaplutoniten, welche im Pan-Afrikanischen Granit-Batholith von Zentral-Kamerun vorkommen (in der Region von Bafia und Adamaoua); (2) einen Schiefer-Gürtel neoproterozoischen Alters, der die Becken von Poli, Lom und Yaoundé beinhaltet, und (3) Pan-Afrikanische (Meta-)Granitoide. Untersuchungen im nördlichen (Region von Poli), südlichen (Region von Yaoundé) und östlichen (Region von Lom-Ngaoundere) zeigen, dass die geodynamische Entwicklung durch Überschiebungs und Blatterverschiebungstektonik charakterisiert ist. Im nördlichen NFBC existieren E-W streichende, flach einfallende Foliationen, welche während der Überschiebung des NFBC auf den Kongo-Kraton entstanden. Im westlichen NFBC existieren vor allem geochemische und petrologische Daten. Die regionale Geologie wird hier durch Pan-Afrikanisches grundgebirge bestimmt, welches aus Graniten und Metamorphiten besteht, die wiederum von känozoischen Magmatiten (Granite, Vulkanite) durchsetzt bzw. überlagert werden. Vorhandene Daten zu Pan-Afrikanischen Plutonen des Untersuchungsgebiets und angrenzenden Regionen zeigen, dass in vielen Regionen ein große Variabilität hinsichtlich des Gesteinschemismus vorliegt, welche von basischen bis hin zu granitischen Gesteinen reicht, wobei der geochemische Charakter i.d.R. kalkalkalin bis alkalin ist. Das initiale Strontium-Verhältnis und Sm-Nd Daten einiger Granite indizieren eine Aufschmelzung im Mantel bei anschließender Kontamination durch kontinentale Kruste. Aufgrund der Anfälligkeit der Rb-Sr Methode existieren kaum verlässliche Alter von Granitoiden des NFBC. Durch die großen Fehler der Rb-Sr Alter sind neben den Platznahmealtern auch die Zeitpunkte der vorhandenen Wiederaufschmelzung weit gehend unbekannt. Durch detaillierte Geländearbeit gelang eine Gliederung des Areals in verschiedene Teilkomplexe. Diese sind der Migmatit-Komplex von Foumbot (MCF), der Bangwa-Komplex (BC), der Komplex von Chepang (CC) und der jüngeren Batié-Pluton (BP), welcher die übrigen Komplexe diskordant durchschlägt. Der BP selbst wird vom känozoischen Batcha Pluton durchsetzt. Innerhalb des MCF existiert eine bedeutende ENE-WSW streichende Scherzone. Im zentralen und südlichen Arbeitsgebiet reichen NE-SW streichende Scherzonen in den BP sowie in den CC und den BC hinein. Der MCF besteht aus Diatexit, Metatexit und Amphibolit. Merkmale wie Scherfaltung älterer Gefüge entlang ENE-WSW streichender Scherflächen und progressive Leukosombildung im Bereich der Faltenscharniere machen deutlich, dass partielle Aufschmelzung mit zunehmender Deformation einhergeht. Bereiche mit hoher Strain-magnitude zeigen koaxiale Plättung an. Die ENE-WSW verlaufende Scherzone weist dextrale Kinematik auf, wobei ältere sinistrale Bewegungen nicht ausgeschlossen werden können. Einzelzirkone von Diatexiten der MCF wurden mittels LA-ICPMS datiert. Mindestens drei Altersdomänen wurden dabei identifiziert: (a) elongierte bis gerundete Zirkon-Kerne mit Altern um 671 ±6 Ma; (b) oszillierend zonierte Zirkon-Mäntel, wahrscheinlich magmatischen Ursprungs, mit einem Alter von 639 ±5 Ma, interpretiert als das Intrusionsalter des Diatexits; (c) rekristallisierte Zirkon-Ränder mit einem Alter von 597 ±6 Ma, welches vermutlich die Metamorphose und Anatexis datiert. Der BC setzt sich aus unterschiedlich stark deformiertem Quarz-Diorit, Granodiorit, Syenogranit, Leucogranit und Monzonit zusammen. Quarz-Diorit und Granodiorit erscheinen in Form von cm- bis m-mächtigen foliierten Körpern. Die Foliation ist im Osten subhorizontal, gen Westen aber fällt sie zunehmend steil nach NE ein. Syenogranit und Leukogranit bilden größere Körper und weisen eine steile, nach NE einfallende, submagmatische Foliation auf. Innerhalb der (Syeno)granite weisen kristallplastische Verformung und Rekristallisation von Feldspat sowie vorhandene S-C Gefüge auf eine Deformation im Subsolidusbereich, d.h. während der Abkühlung, hin. Die aus den Mikrogefügen abgeleiteten Deformationsmechanismen charakteristischer Minerale der Quarz-Diorite und Granodiorite deuten hingegen auf Verformung unter Bedingungen einer hoch- und niedriggradigen Metamorphose hin. Innerhalb NE-SW verlaufender Mylonite am Kontakt BC/BP wird ein dextraler Schersinn durch S-C Gefüge angezeigt. In den zentralen Bereichen des BC sind Überprägungen sinistraler durch dextrale Scherzonen hingegen nur lokal sichtbar. Die Phengit-Zusammensetzung deformierter Gesteine deutet auf Scherung bei einem Maximaldruck von ca. 4.5 kbar bei T = ca. 500 °C hin. Die östlichen Nebengesteine des BC in der Region von Maham sind Migmatite, deren subhorizontale Foliation in zunehmendem Maße in wenige cm bis einige m mächtige ENE-WSW streichende Scherzonen übergeht. Die Gefüge der Migmatite der Region von Maham und (grano)dioritischer Gesteine des BC deuten auf eine regionale Überschiebungstektonik mit SSE gerichtetem Deckentransport hin. Die Zirkon- und Monazitalter deuten auf zwei Altersgruppen innerhalb des BC hin mit jeweils unterschiedlichen Platznahmealtern. Die ältere Gruppe besteht aus Quarzdiorit (643 ±5 Ma und 641 ±4 Ma, LA-ICPMS Daten, U-Pb Zirkonalter) und Granodiorit (638 ±2 Ma, IDTIMS Daten; 641 ±8 Ma und 641 ±2 Ma, LA-ICPMS Daten; U-Pb Zirkonalter), die jüngere Gruppe umfasst Syenogranit (598 ±21 Ma, 605 ±11 Ma, EMP Daten, U-Th-Pb Monazitalter) und Leukogranit (607 ±3 Ma und 603 ±4 Ma, LA-ICPMS Daten; U-Pb Zirkonalter). 206Pb/238U Alter zwischen 656 ±9 Ma und 718 ±13 Ma wurden an Zirkonkernen des Granodiorits bestimmt. Eine Regressionsgerade durch alle analysierten Kerne ergibt ein oberes Schnittpunktalter von 672 ±8 Ma. Der CC wird von im m-Maßstab wechselnden Lagen dioritischer und granitischer Zusammensetzung aufgebaut. Eine mylonitische Foliation streicht NE-SW. S-L-gefüge und Quarz-[c]-Achsen Verteilungen weisen auf Plättung unter hochgradigen Bedingungen (T = 650 °C) hin. Phengit-Barometrie mylonitisierter Granite ergibt einen Maximaldruck von 6 kbar bei T = ca. 500°C. Radiometrische Untersuchungen des mylonitischen Granits des CC wurden mittels LAICPMS an Zirkon und Monazit sowie mit Elektronenstrahlmikrosonde (EMP) an Monazit durchgeführt. Das EMP Monazit Alter (621 ±33 Ma) und LA-ICPMS Alter (622 ±13, oberes Schnittpunktalter; 611 ±4 und 608 ±6 Ma, gewichtete Mittelwerte der 208Pb/232Th und 207Pb/238U Alter) stehen im Einklang mit dem konkordanten LA-ICPMS Zirkonalter (611 ±5 Ma). Letzteres wird als Intrusionsalter des Granits interpretiert. Der BP wird im Wesentlichen von mittel- bis grobkörnigem Syenogranit aufgebaut. Speziell im Randbereich werden magmatische Gefüge (Fließgefüge, Aggregate von xenomorphem Quarz) durch submagmatische Gefüge überprägt und schließlich ersetzt (kristallplastische Deformation und Rekristallisation von Quarz und Feldspat, Bildung von Myrmekiten und S-C Gefügen). Sowohl die vom magmatischen bis in das Subsolidus-Stadium anhaltende Deformation, als auch die Parallelität der steil einfallenden postmagmatischen Foliation im Randbereich des BP und den angrenzenden BC, CC und MCF weisen auf eine synkinematische Platznahme des BP entlang krustaler Blattverschiebungen hin. Ein Konkordiaalter von 602 ±1.4 Ma wurde mit der ID-TIMS Methode erhalten. Mittels LAICPMS wurde ein Alter von 599 ±13 Ma (oberes Schnittpunktalter) bestimmt, welches im Fehler dem ID-TIMS Konkordia-Alter gleicht. Letzteres wird als Platznahmealter interpretiert. Die Kombination geochronologischer und struktureller Daten erlaubt die Unterscheidung von insgesamt drei tektono-magmatischen Abschnitten: Phase I ist durch die Platznahme dioritischer und granodioritischer Gesteine des BC sowie der Protolithe der Migmatite des MCF bei etwa 640 Ma charakterisiert. Während Phase II bei ca. 607 Ma intrudierten Syenogranit und Leukogranite in den BC und der Granits des CC. Gleichzeitig unterlagen die 640 Ma alten Granite einer hochgradigen Metamorphose. Die Intrusion der 607 Ma alten Plutonite geht einher mit einem Wechsel von Überschiebungstektonik hin zu sinistraler Blatterverschiebungstektonik. Die Platznahme des porphyritischen Syenogranits von Batié vor ca. 600 Ma, welche dextrale Bewegungen im Randbereich des BP und unmittelbar angrenzender Nebengesteine auslöste, stellt die dritte tektono-magmatische Phase dar. Alter von 700 bis 660 Ma, bestimmt an Zirkonkernen der Migmatite des MCF und der Granodiorite des BC, indizieren eine Platznahme der ältesten Granite in Pan-Afrikanischem Basement. Einige ererbte Zirkonkerne paläoproterozoischen Alters innerhalb des Leukogranits des BC deuten auf die Beteiligung Eburnischer Kruste in der Entwicklung der Pan-Afrikanischen Granite hin. Die neuen Daten bestätigen bisherige Vermutungen, dass der westliche NFBC ein afrikanisches Äquivalent zur Borborema Provinz Brasiliens darstellt. Auffällig sind geochronologische Übereinstimmungen bei den (Meta)granitoiden und den prä- bis synkinematischen Brasiliano Granitoiden der Borborema Provinz. Auf der anderen Seite ist speziell in der späten Entwicklung ab ca. 600 Ma die Kinematik blattverschiebender Bewegungen teilweise unterschiedlich. Eine mögliche Ursache sind lokale Variationen im Stressfeld, bedingt durch die Platznahme der syn- bis spät-tektonischen Magmatite.
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.
The present study was elaborated within the scope of the INTAFERE (Integrated Analysis of Mobile Organic Foreign Substances in Rivers) project which investigates the occurrence of xenobiotics in small freshwater streams with particular consideration of social impact factors. The aim of this study is to investigate the seasonal and spatial variance of organic micropollutants in small fresh water streams and to identify possible sources and sinks. Therefore four small freshwater river systems in Hesse, Germany, have been investigated with respect to common organic pollutants such as: the organophosphates tri-n-butyl phosphate (TBP), tris(2-butoxyethyl)phosphate (TBEP), tris(2-chloroethyl)phosphate (TCEP), tris(1-chloro-2-propyl)phosphate (TCPP), and tris(1,3-dichloro-2-propyl)phosphate (TDCPP), the synthetic musk fragrances 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexa-methylcyclopenta-[g]-2-benzopyran (HHCB) and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN), the endocrine disruptors bisphenol A (BPA), 4-tert-octylphenol (OP) and the technical isomer mixture of 4-nonylphenol (NP), the herbicide terbutryn [2-(t-butylamino)-4-(ethylamino)-6-(methylthio)-s-triazine] as well as the insect repellent N,N-diethyl-m-toluamide (DEET). Water samples were collected in the time span from September 2003 to September 2006 at 26 sampling locations. The samples were extracted with solid phase extraction (SPE) and analyzed by coupled gas chromatography-mass spectrometry (GC-MS). For quantification the internal standard method was used. The results of the study showed an ubiquitous occurrence of organic pollutants in the fresh water streams of the study area. The organophosphates have been detected in 90 % of the water samples with mean concentrations of 502 ng/l (TCPP), 276 ng/l (TBP), 183 ng/l (TBEP), 118 ng/l (TCEP) and 117 ng/l (TDCPP). Sewage treatment plant (STP) effluents were identified as the dominating source for the chlorinated organophosphates as well as for the synthetic musk fragrances and the insect repellent DEET in the river systems. Consequently the highest concentrations were observed in the Schwarzbach system characterized by the highest proportion of waste water compared to the other river systems. Mean concentration levels of the synthetic musk fragrances HHCB and ATHN were 141 ng/l and 46 ng/l, respectively and 124 ng/l in case of DEET. The synthetic musk fragrances showed a clear seasonal trend with significantly lower concentrations in summer times compared to winter times, which is ascribed to stronger photodegradation and volatization during summer times. In contrast, mean DEET concentrations and loads were significantly higher in summer than in autumn, winter and spring, in parallel with the main insect season. The concentrations of the endocrine disruptors BPA, NP and OP in the river water samples ranged from <20 ng/l to 1927 ng/l, <10 ng/l to 770 ng/l, and <10 ng/l to 420 ng/l, respectively. Whereas OP was present in about 2/3 of the samples, NP and BPA could only be detected in 56% and 13% of the water samples, respectively. BPA levels exceeded in two samples the predicted no-effect concentration (PNEC) for water organisms. In case of NP, highest concentrations and loads were found in September 2003 and decreased significantly since then. In contrast, concentrations and loads of OP which serves in a similar application field remained nearly constant during the sampling period. The decrease of NP can be attributed to the implementation of the European Directive 2003/53/EG, which restricts the use of nonylphenols and nonylphenol ethoxylates since January 2005. However, at the end of the sampling period in September 2006, NP could still be detected at mean concentrations of 18 ng/l in the river waters of the sampling area. Furthermore, absence of NP in several samples from associated STP effluents indicate that the STPs cannot be the only sources for NP found in the river water. The herbicide terbutryn was present in the rivers during the whole sampling period from September 2003 to September 2006 despite a ban on its use as a herbicide from January 2004 on. Terbutryn levels ranged from < 4 ng/l to 5600 ng/l, showing a clear spatial pattern with high terbutryn concentrations in the Weschnitz and Modau river systems and significantly lower terbutryn levels in Schwarzbach and Winkelbach. Results from the analysis of two STP effluents discharging into the Weschnitz and the Modau, respectively, indicate that terbutryn enters the rivers from this source. Furthermore, terbutryn concentrations and loads showed a clear seasonal trend with significantly higher levels in summer and autumn. Obviously, the ban on agricultural use of terbutryn at the end of 2003 had no discernable influence on terbutryn concentration in the rivers because there was no trend of decreasing.