Variation of stable silicon isotopes: Analytical developments and applications in Precambrian geochemistry

Die vorliegende Dissertation behandelt die Gesamtgesteinsanalyse stabiler Siliziumisotope mit Hilfe einer „Multi Collector-ICP-MS“. Die Analysen fanden in Kooperation mit dem „Royal Museum for Central Africa“ in Belgien statt. Einer der Schwerpunkte des ersten Kapitels ist die erstmalige Analyse des δ30Si –Wertes an einem konventionellen Nu PlasmaTM „Multi-Collector ICP-MS“ Instrument, durch die Eliminierung der den 30Si “peak” überlagernden 14N16O Interferenz. Die Analyse von δ30Si wurde durch technische Modifikationen der Anlage erreicht, welche eine höherer Massenauflösung ermöglichten. Die sorgsame Charakterisierung eines adäquaten Referenzmaterials ist unabdingbar für die Abschätzung der Genauigkeit einer Messung. Die Bestimmung der „U.S. Geological Survey“ Referenzmaterialien bildet den zweiten Schwerpunkt dieses Kapitales. Die Analyse zweier hawaiianischer Standards (BHVO-1 and BHVO-2), belegt die präzise und genaue δ30Si Bestimmung und bietet Vergleichsdaten als Qualitätskontrolle für andere Labore. Das zweite Kapitel befasst sich mit kombinierter Silizium-/Sauerstoffisotope zur Untersuchung der Entstehung der Silizifizierung vulkanischer Gesteine des „Barberton Greenstone Belt“, Südafrika. Im Gegensatz zu heute, war die Silizifizierung der Oberflächennahen Schichten, einschließlich der „Chert“ Bildung, weitverbreitete Prozesse am präkambrischen Ozeanboden. Diese Horizonte sind Zeugen einer extremen Siliziummobilisierung in der Frühzeit der Erde. Dieses Kapitel behandelt die Analyse von Silizium- und Sauerstoffisotopen an drei unterschiedlichen Gesteinsprofilen mit unterschiedlich stark silizifizierten Basalten und überlagernden geschichteten „Cherts“ der 3.54, 3.45 und 3.33 Mill. Jr. alten Theespruit, Kromberg und Hooggenoeg Formationen. Siliziumisotope, Sauerstoffisotope und die SiO2-Gehalte demonstrieren in allen drei Gesteinsprofilen eine positive Korrelation mit dem Silizifizierungsgrad, jedoch mit unterschiedlichen Steigungen der δ30Si-δ18O-Verhältnisse. Meerwasser wird als Quelle des Siliziums für den Silizifizierungsprozess betrachtet. Berechnungen haben gezeigt, dass eine klassische Wasser-Gestein Wechselwirkung die Siliziumisotopenvariation nicht beeinflussen kann, da die Konzentration von Si im Meerwasser zu gering ist (49 ppm). Die Daten stimmen mit einer Zwei-Endglieder-Komponentenmischung überein, mit Basalt und „Chert“ als jeweilige Endglieder. Unsere gegenwärtigen Daten an den „Cherts“ bestätigen einen Anstieg der Isotopenzusammensetzung über der Zeit. Mögliche Faktoren, die für unterschiedliche Steigungen der δ30Si-δ18O Verhältnisse verantwortlich sein könnten sind Veränderungen in der Meerwasserisotopie, der Wassertemperatur oder sekundäre Alterationseffekte. Das letzte Kapitel beinhaltet potentielle Variationen in der Quellregion archaischer Granitoide: die Si-Isotopen Perspektive. Natriumhaltige Tonalit-Trondhjemit-Granodiorit (TTG) Intrusiva repräsentieren große Anteile der archaischen Kruste. Im Gegensatz dazu ist die heutige Kruste kaliumhaltiger (GMS-Gruppe: Granit-Monzonite-Syenite). Prozesse, die zu dem Wechsel von natriumhaltiger zu kaliumhaltiger Kruste führten sind die Thematik diesen Kapitels. Siliziumisotopenmessungen wurden hier kombiniert mit Haupt- und Spurenelementanalysen an unterschiedlichen Generationen der 3.55 bis 3.10 Mill. Yr. alten TTG und GMS Intrusiva aus dem Arbeitsgebiet. Die δ30Si-Werte in den unterschiedlichen Plutonit Generationen zeigen einen leichten Anstieg der Isotopie mit der Zeit, wobei natriumhaltige Intrusiva die niedrigste Si-Isotopenzusammensetzung aufweisen. Der leichte Anstieg in der Siliziumisotopenzusammensetzung über die Zeit könnte auf unterschiedliche Temperaturbedingungen in der Quellregion der Granitoide hinweisen. Die Entstehung von Na-reichen, leichten d30Si Granitoiden würde demnach bei höheren Temperaturen erfolgen. Die Ähnlichkeit der δ30Si-Werte in archaischen K-reichen Plutoniten und phanerozoischen K-reichen Plutoniten wird ebenfalls deutlich.

Mediterranean-type climate in the South Aegean (Eastern Mediterranean) during the Late Miocene: Evidence from isotope and element proxies

The present-day climate in the Mediterranean region is characterized by mild, wet winters and hot, dry summers. There is contradictory evidence as to whether the present-day conditions (“Mediterranean climate”) already existed in the Late Miocene. This thesis presents seasonally-resolved isotope and element proxy data obtained from Late Miocene reef corals from Crete (Southern Aegean, Eastern Mediterranean) in order to illustrate climate conditions in the Mediterranean region during this time. There was a transition from greenhouse to icehouse conditions without a Greenland ice sheet during the Late Miocene. Since the Greenland ice sheet is predicted to melt fully within the next millennia, Late Miocene climate mechanisms can be considered as useful analogues in evaluating models of Northern Hemispheric climate conditions in the future. So far, high resolution chemical proxy data on Late Miocene environments are limited. In order to enlarge the proxy database for this time span, coral genus Tarbellastraea was evaluated as a new proxy archive, and proved reliable based on consistent oxygen isotope records of Tarbellastraea and the established paleoenvironmental archive of coral genus Porites. In combination with lithostratigraphic data, global 87Sr/86Sr seawater chronostratigraphy was used to constrain the numerical age of the coral sites, assuming the Mediterranean Sea to be equilibrated with global open ocean water. 87Sr/86Sr ratios of Tarbellastraea and Porites from eight stratigraphically different sampling sites were measured by thermal ionization mass spectrometry. The ratios range from 0.708900 to 0.708958 corresponding to ages of 10 to 7 Ma (Tortonian to Early Messinian). Spectral analyses of multi-decadal time-series yield interannual δ18O variability with periods of ~2 and ~5 years, similar to that of modern records, indicating that pressure field systems comparable to those controlling the seasonality of present-day Mediterranean climate existed, at least intermittently, already during the Late Miocene. In addition to sea surface temperature (SST), δ18O composition of coral aragonite is controlled by other parameters such as local seawater composition which as a result of precipitation and evaporation, influences sea surface salinity (SSS). The Sr/Ca ratio is considered to be independent of salinity, and was used, therefore, as an additional proxy to estimate seasonality in SST. Major and trace element concentrations in coral aragonite determined by laser ablation inductively coupled plasma mass spectrometry yield significant variations along a transect perpendicular to coral growth increments, and record varying environmental conditions. The comparison between the average SST seasonality of 7°C and 9°C, derived from average annual δ18O (1.1‰) and Sr/Ca (0.579 mmol/mol) amplitudes, respectively, indicates that the δ18O-derived SST seasonality is biased by seawater composition, reducing the δ18O amplitude by 0.3‰. This value is equivalent to a seasonal SSS variation of 1‰, as observed under present-day Aegean Sea conditions. Concentration patterns of non-lattice bound major and trace elements, related to trapped particles within the coral skeleton, reflect seasonal input of suspended load into the reef environment. δ18O, Sr/Ca and non-lattice bound element proxy records, as well as geochemical compositions of the trapped particles, provide evidence for intense precipitation in the Eastern Mediterranean during winters. Winter rain caused freshwater discharge and transport of weathering products from the hinterland into the reef environment. There is a trend in coral δ18O data to more positive mean δ18O values (–2.7‰ to –1.7‰) coupled with decreased seasonal δ18O amplitudes (1.1‰ to 0.7‰) from 10 to 7 Ma. This relationship is most easily explained in terms of more positive summer δ18O. Since coral diversity and annual growth rates indicate more or less constant average SST for the Mediterranean from the Tortonian to the Early Messinian, more positive mean and summer δ18O indicate increasing aridity during the Late Miocene, and more pronounced during summers. The analytical results implicate that winter rainfall and summer drought, the main characteristics of the present-day Mediterranean climate, were already present in the Mediterranean region during the Late Miocene. Some models have argued that the Mediterranean climate did not exist in this region prior to the Pliocene. However, the data presented here show that conditions comparable to those of the present-day existed either intermittently or permanently since at least about 10 Ma.

Exploring physical processes related to past climate proxies: lake sediments and stable water isotopes

Proxy data are essential for the investigation of climate variability on time scales larger than the historical meteorological observation period. The potential value of a proxy depends on our ability to understand and quantify the physical processes that relate the corresponding climate parameter and the signal in the proxy archive. These processes can be explored under present-day conditions. In this thesis, both statistical and physical models are applied for their analysis, focusing on two specific types of proxies, lake sediment data and stable water isotopes.rnIn the first part of this work, the basis is established for statistically calibrating new proxies from lake sediments in western Germany. A comprehensive meteorological and hydrological data set is compiled and statistically analyzed. In this way, meteorological times series are identified that can be applied for the calibration of various climate proxies. A particular focus is laid on the investigation of extreme weather events, which have rarely been the objective of paleoclimate reconstructions so far. Subsequently, a concrete example of a proxy calibration is presented. Maxima in the quartz grain concentration from a lake sediment core are compared to recent windstorms. The latter are identified from the meteorological data with the help of a newly developed windstorm index, combining local measurements and reanalysis data. The statistical significance of the correlation between extreme windstorms and signals in the sediment is verified with the help of a Monte Carlo method. This correlation is fundamental for employing lake sediment data as a new proxy to reconstruct windstorm records of the geological past.rnThe second part of this thesis deals with the analysis and simulation of stable water isotopes in atmospheric vapor on daily time scales. In this way, a better understanding of the physical processes determining these isotope ratios can be obtained, which is an important prerequisite for the interpretation of isotope data from ice cores and the reconstruction of past temperature. In particular, the focus here is on the deuterium excess and its relation to the environmental conditions during evaporation of water from the ocean. As a basis for the diagnostic analysis and for evaluating the simulations, isotope measurements from Rehovot (Israel) are used, provided by the Weizmann Institute of Science. First, a Lagrangian moisture source diagnostic is employed in order to establish quantitative linkages between the measurements and the evaporation conditions of the vapor (and thus to calibrate the isotope signal). A strong negative correlation between relative humidity in the source regions and measured deuterium excess is found. On the contrary, sea surface temperature in the evaporation regions does not correlate well with deuterium excess. Although requiring confirmation by isotope data from different regions and longer time scales, this weak correlation might be of major importance for the reconstruction of moisture source temperatures from ice core data. Second, the Lagrangian source diagnostic is combined with a Craig-Gordon fractionation parameterization for the identified evaporation events in order to simulate the isotope ratios at Rehovot. In this way, the Craig-Gordon model can be directly evaluated with atmospheric isotope data, and better constraints for uncertain model parameters can be obtained. A comparison of the simulated deuterium excess with the measurements reveals that a much better agreement can be achieved using a wind speed independent formulation of the non-equilibrium fractionation factor instead of the classical parameterization introduced by Merlivat and Jouzel, which is widely applied in isotope GCMs. Finally, the first steps of the implementation of water isotope physics in the limited-area COSMO model are described, and an approach is outlined that allows to compare simulated isotope ratios to measurements in an event-based manner by using a water tagging technique. The good agreement between model results from several case studies and measurements at Rehovot demonstrates the applicability of the approach. Because the model can be run with high, potentially cloud-resolving spatial resolution, and because it contains sophisticated parameterizations of many atmospheric processes, a complete implementation of isotope physics will allow detailed, process-oriented studies of the complex variability of stable isotopes in atmospheric waters in future research.rn