Fire plays an important role in the earth system by influencing ecosystems and climate, but climate in turn also influences fire. The system became more complex when humans started using fire as a tool. Understanding the interaction between humans, fire and climate is the major aim of paleofire research. Understanding changes in these three aspects in the past will help predicting future climate, fire and human interactions. The use of lake sediment cores as natural archives for reconstructing past fire activity by counting charcoal particles is well established. This present dissertation is dedicated to the evaluation and application of specific organic molecular markers for biomass burning: levoglucosan, mannosan and galactosan were used as proxies for reconstructing past fire activity in lake sediments thorough the entire Holocene. First, a new analytical method was developed using high-performance anion exchange chromatography combined with mass spectrometry to separate and detect these three monosaccharide anhydrides in lake sediments. The suitability of this analytical method was proven by comparing the levoglucosan, mannosan and galactosan results in selected lake sediment samples from Lake Kirkpatrick, New Zealand and by correlating the results with macroscopic charcoal. Furthermore, the method was successfully applied to a lake sediment core from Lake Petén Itzá, Guatemala to reconstruct regional Holocene fire history. The analyses of levoglucosan were combined with fecal sterols to reconstruct late Holocene human fire interactions at Lake Trasimeno, Italy, demonstrating low fire activity during the Roman period. This combination of studies proves that these molecular markers are valid fire proxies in sediments from multiple locations around the globe. Comparison of levoglucosan, mannosan and galactosan concentrations with macroscopic charcoal trends in Lake Kirkpatrick and Lake Petén Itzá, suggests that the molecular markers represent more regional fire history and low temperature fires in contrast to macroscopic charcoal, which is a local fire proxy. In addition, vegetation changes (Lake Kirkpatrick and Lake Petén Itzá) and charcoal morphotypes (Lake Petén Itzá) were compared to the levoglucosan/mannosan and levoglucosan/(mannosan+galactosan) ratios suggesting that these ratios may be a suitable tool to track burned fuel. Biodegradation tests demonstrate the potential degradation of levoglucosan, mannosan and galactosan if dissolved in water, but findings in ancient sediment samples suggest that particle-bound levoglucosan, mannosan and galactosan can be buried in sediments over millennial time scales. Although uncertainties still exist, the results of this research suggests that organic molecular markers are a suitable regional fire proxy and isomer ratios may help understand changes in burned vegetation.
Der hochwassergebundene Sedimenteintrag ist Motor der Bodenbildung in Auen. Der mit dem Sedimenteintrag einhergehende Schadstofftransport in die flussbegleitenden Auen ist Ursache für die Akkumulation von Schadstoffen in den aquatischen und semiterretrischen Systemen. Er wirkt in weiten Teilen der Elbauen nicht nur einschränkend auf die landwirtschaftliche Nutzung des Grünlandes sondern beeinträchtigt daneben auch weitere Schutzgüter, wie z. B. Habitate und Lebensgemeinschaften. Diese Arbeit hatte das Ziel, die Steuergrößen des Sediment- und Schadstoffeintrags anhand von langjährig erhobenen Messdaten zu untersuchen und gleichzeitig die zeitliche und räumliche Verbreitung ausgewählter Schadstoffe als Baustein eines belastungsangepassten Auenmanagements aufzuklären. Dafür wurden eigene Daten über Hochflutsedimente und Böden ebenso ausgewertet wie Daten anderer Autoren. Außerdem lag ein Schwerpunkt der Arbeit in der kombinierten Auswertung von Zeitreihen der Sedimentbelastung von Gewässern und von Auenböden, die eine Grundlage für das Verständnis des elbespezifischen Belastungsmosaiks von Böden mit Schwermetallen und Dioxinen/Furanen darstellt. Zunächst erfolgte eine detaillierte Recherche und Analyse der retentionsfördernden Eigenschaften der Elbauen. Es wurden abschnittsspezifische Flächengrößen, Landnutzungsunterschiede und Flächenbetroffenheiten bei unterschiedlichen Hochwasserzuständen herausgearbeitet. Mit Hilfe der darauf aufbauenden, datenbasierten Analysen über ereignisbezogene Sedimenteinträge in die Elbauen konnten wesentliche Steuergrößen des Sedimenteintrags identifiziert werden. Die Distanz der Standorte zur Elbe ist die wesentliche Kenngröße, sodass die größten Sedimenteinträge in Flussnähe stattfinden. Darüber hinaus ist die Höhe des Sedimenteintrags abflussabhängig. Auf dieser Grundlage wurde ein Ansatz zur Berechnung des großräumigen Sedimenteintrags entwickelt, mit dessen Hilfe die Retentionsfunktion der Auen im Abfluss- und Stofftransportgeschehen der Elbe abgeschätzt werden konnte. Die Sedimentretention der Elbauen hatte im Betrachtungszeitraum zwischen 2003 und 2008 einen Anteil von 7 bis 30 % an den Jahresschwebstofffrachten in Hitzacker. Die Analysen von verschiedenen Zeitreihen der Sediment- und Bodenbelastungen mit Schwermetallen, Arsen sowie Dioxinen/Furanen verdeutlichte, dass die Stoffgruppen ganz unterschiedliche Belastungsentwicklungen durchlaufen haben. Der Schwerpunkt der Dioxinkontamination in Sedimenten und Böden trat in den 1950er bis 1960er Jahren auf, während Metalle im Allgemeinen erst später Belastungsmaxima zeigten. Allerdings konnte mit dem Pb/Zn-Verhältnis ein Metallmuster identifiziert werden, mit dessen Hilfe auch in Oberböden auf der Basis von Metalldaten auf Dioxinbelastungen geschlossen werden konnte. Darüber hinaus wurde unter Kenntnis der spezifischen Belastungshistorien mittels Kategorisierung der Standorteigenschaften Höhenlage, Distanz, Bioturbation und Sedimenteintrag ein Erklärungsschema zur Vorhersage von räumlichen Schadstoffmustern für ausgewählte Metalle und Dioxine/Furane entwickelt. Sowohl die Untersuchungen zum Sedimentationsgeschehen als auch zur Aufklärung des Belastungsmosaiks in den Elbauen ließen Ableitungen von Maßnahmenvorschlägen zur Förderung der Sedimentationsdynamik, des Hochwasserschutzes, zur schadstoffspezifischen Verbesserung der Bodenbelastung als auch zur belastungsangepassten Landnutzung zu.
Among all attenuation processes, biodegradation plays one of the most important role and is one of the most desirable processes in the environment. To assess biodegradation, a variety of biodegradation test procedures have been developed by several international organizations. OECD guidelines for ready biodegradability testing represent one of the most prominent group of internationally used screening biodegradation tests (series 301A-F). These tests are usually very simple in their designs and allow for the fast and cheap screening of biodegradability. However, because of their stringency, the test conditions are not close to simulating environmental conditions and may lead to unrealistic results. To overcome these limitations, OECD introduced simulation tests which are designed to investigate the behavior of chemicals in specified environmentally relevant compartments. Despite the fact that simulation tests give more insight into the fate of chemicals in the environment, they are not applied frequently as they are often tedious, time consuming and expensive. Consequently, there is a need to provide a new biodegradation testing method that would combine complex testing environment as in simulation tests, easiness in handling and good data repeatability as in screening biodegradation tests. Another challenge is an adaption of the existing biodegradation testing methods to new types of samples, i.e. mixtures of transformation products (TPs). The research on the presence of pharmaceuticals in the environment gained momentum in the 1990s; since then, it has been growing. Their presence in the environment is a wellestablished fact. A wide range of pharmaceuticals is continuously detected in many environmental compartments such as surface waters, soils, sediments, or ground waters. After pharmaceuticals reach the natural aquatic environment they may undergo a number of processes such as: photolysis (under direct sunlight), hydrolysis, oxidation and reduction reactions, sorption, biodegradation (by bacteria of fungi), and bioaccumulation. These processes, may cause their elimination from aquatic environment, if reaction is complete, or creation of new compounds i.e., transformation products (TPs). What is more, processes, like chlorination and advanced oxidation processes (AOPs), such as H2O2/UV, O3/UV, TiO2/UV, Fenton, and photo-Fenton, or UV treatment which might be applied in water or wastewater treatment, may also lead to the TPs introduction into aquatic environment. The research on the TPs brings many new challenges. From one side, there is a constant need for the the development of a sensitive and reliable analytical separation, detection, and structure elucidation methods. Additionally, there is a need for the preparation of appropriate assays for the investigation of properties of new compounds, especially those answering the question if TPs pose a higher risk to the aquatic ecosystems than their parent compounds. Among numerous groups of pharmaceuticals, two are of great importance: antibiotics since they might promote emergence and maintenance of antimicrobial resistance in the aquatic environment; and cytostatic drugs. Cytostatic drugs can exert carcinogenic, mutagenic and/or teratogenic effects in animals and humans. The challenges of biodegradation testing presented in this thesis, encompasses these different areas of interest and was divided into three objectives: 1) Identification of the knowledge gaps and data distribution of the two groups of pharmaceuticals antibiotics and cytostatic drugs (article I); 2) Increasing the knowledge on biodegradation of cytostatic drugs and their TPs (articles II, III, and IV) and 3) Establishment of a biodegradation test with closer to simulation tests conditions, that could be affordable and to support better understanding on processes in water sediment interface construction - screening water-sediment test. Further validation of the test with an insight into sorption and desorption processes (articles V and VI).
In this dissertation, a multi-proxy study, which included palaeoecological, lithological, geochemical and geochronological methods, was carried out to investigate climatic and environmental changes and their interaction during the Quaternary in formerly glaciated and non-glaciated areas. The information obtained will be used to provide a better understanding of the regional stratigraphic framework and to establish broader regional terrestrial correlations within the global marine isotope stage (MIS) framework. This study was conducted on two key drillings, the Garding-2 research drill core in the German North Sea coastal area of Schleswig-Holstein and the GBY#2 archaeological core at the Gesher Benot Ya´aqov (GBY) site, in the Upper Jordan Valley in Israel. The results of this study are presented in three papers. Papers I and II focus on the study of the Garding-2 core, while the multi-proxy study of the GBY#2 core is presented in Paper III. The results of a variety of analyses conducted on the 240 m long Garding-2 sequence show interglacial-glacial cycles that are mainly controlled by variations in temperature. This sequence is composed of mainly fluvial-shallow marine sediments intercalated by muddy-peaty deposits. Based on the palynological and lithological findings, the Pliocene-Pleistocene transition was observed at 182.87 m. It is overlain by Praetiglian and the subsequent sediments of the Waalian and Bavelian Complexes. The boundary of either the second or third Cromerian Interglacial with younger sediments, which still belong to MIS 19, is marked by the last occurrence of Tsuga at 119.50 m and the development of mixed-deciduous forests. The palynologically equivalent sediments of the Bilshausen Interglacial were found below two Elsterian till layers, at 89.00 m-82.00 m. These sediments showed high and increased percentages of Pinus and Picea and scattered occurrences of Abies and Carpinus, which are similar to the features of the beginning of the Bilshausen or Rhume interglacial (Müller, 1992). An unconformity occurred at 80.29 m, at the bottom of late Holsteinian deposits, characterised by the occurrences of Fagus and Pterocarya, with low percentages of Abies and Carpinus and the absence of Buxus. These deposits are succeeded by sediments of the Fuhne cold period that shows higher percentages of NAP and occurrences of Ericales, Helianthemum and Selaginella selaginoides, which are unconformably overlain by Drenthian till at 73.00 m-71.00 m. A single peaty sample at 69.25 m with Pinus-Picea-Abies assemblage is correlated with the late Eemian Interglacial. This deposit is overlain by Weichselian glaciofluvial sediments. Middle-late Holocene sediments occurred from 20 m upwards, following a hiatus, which was caused by the Early Holocene transgression. A subsequent thin layer of marine Atlantic sediments is unconformably overlain by marine-tidal flat deposits up to 11.00 m. The first occurrence of Fagus (at 15.97 m) and Carpinus (at 15.03 m), which was optically stimulated luminescence (OSL)-dated to 3130 +/- 260 BP (at 16.22 m, Zhang et al., 2014), gives evidence for a Subboreal age for these deposits. Sandy sediments of the early Subatlantic, which were deposited between 11.00 m and the top of the Garding-2 sequence, indicate that local salt marshes, dunes and tidal flat vegetation expanded during this period. Due to regional features and the peculiarities of the local coastal environment, the expansions of Fagus and Carpinus, which are characteristic for the Subboreal-Subatlantic transition at about 2700 BP in northern Germany, are not clearly reflected in the Garding-2 pollen diagram. In the Mediterranean area, a 50 m long core of GBY#2, was drilled at the Acheulian site of Gesher Benot Ya´akov. The GBY#2 core provides a long Early-Middle Pleistocene geological, environmental and climatological record, which also enriches the knowledge of hominin-habitat relationships documented at the margins of the Hula Palaeo-lake. The sediment sequence of GBY#2 is under- and overlain by two basalt flows that are 40Ar/39Ar dated: two samples at the bottom of the core dated to 1195 +/- 67 ka (at 48.30 m) and 1137 +/- 69 ka (at 45.30 m), and another one at the top dated to 659 +/- 85 ka (at 14.90 m). With the additional chronological identification of the Matuyama Brunhes Boundary (MBB) and the correlation with the GBY excavation sites, the sedimentary sequence of GBY#2 provides the climatic history during the late part of the mid-Pleistocene transition (MPT, 1.2 Ma-0.5 Ma). Multi-proxy analyses including those of pollen and non-pollen palynomorphs, macro botanical remains, molluscs, ostracods, fish, amphibians and micromammals provide evidence for lake and lake-margin environments during MIS 20 and MIS 19. During MIS 20, relatively cool semi-moist conditions were followed by a pronounced dry phase. During the subsequent MIS 19, warm and moist interglacial conditions were characterised by Quercus-Pistacia woodlands in this area. The depositional environment changed from an open water lake during MIS 20 to a lake margin environment in MIS 19. This finding is at odds with changing climate conditions from relatively dry to moist. This discrepancy could be explained by the prograding pattern of the lake shore due to the infilling of the basin, which resulted in shallower water. Climatic changes during the Late Tertiary and the Quaternary in the high latitude regions in northwest Europe and during the Early-Middle Pleistocene in the mid latitude regions of the Middle East follow the patterns of global climatic changes, which are mainly controlled by orbital obliquity (+/-41 ka cycle) during the Early Pleistocene and by orbital eccentricity (+/-100 ka cycle) during the MPT (1.2 Ma-0.5 Ma) and the younger periods of the Quaternary. The results of this study also provide reliable evidence for long distance correlation of stratigraphic and climatic events of the Quaternary, which extends knowledge of regional and global impact of climatic fluctuations on the environment.