Geochemistry of Indian Ocean tephra and Afro-Arabian lavas

Widespread silicic pyroclastic eruptions of the Oligocene Afro-Arabian flood volcanic province (ignimbrites and airfall tuffs) produced up to 20% of the total flood volcanic stratigraphy (>6*10**4 km**3). Volumes of individual ignimbrites and tuffs exposed on land range from ~150 to >2000 km**3 and eight major units (15-100 m thick) were erupted in <2 Myr, placing these amongst the largest-magnitude silicic pyroclastic eruptions on Earth. They are compositionally distinctive time-stratigraphic markers which were deposited as co-ignimbrite ashfall deposits on a near-global scale around the time of the Oi2 cooling anomaly at ~30 Ma. Two ignimbrites from the lower part of the flood volcanic succession in Yemen have been correlated to: (a) the conjugate rifted margin of Ethiopia (>500 km distant); and (b) to two deep sea ash layers sampled by ODP Leg 115 in the Indian Ocean ~2700 km to the southeast. This correlation is based on whole rock analyses of silicic units for isotope ratios (Pb, Nd) and rare earth element compositions, in conjunction with novel in situ Pb isotope laser ablation multicollector inductively coupled plasma mass spectroscopy analysis of groundmass and glass shards. Compositional diversity preserved on the scale of individual ash shards in these deep sea tephra layers record chemical heterogeneity present in the silicic magma chambers that is not evident in the welded on-land deposits. Ages of the ash layers can be established by correlation to precisely dated on-land ignimbrites, and current evidence suggests that while these eruptions may have exacerbated already changing climatic conditions, they both marginally post-date the Oi2 global cooling anomaly.

Alkenones in surface waters of the Nordic seas

Samples of filtered particulate organic matter (POM) were obtained during the summers of 1999 and 2000 from the surface waters of the Nordic seas to monitor the spatial distribution of long-chain alkenones. The aim of the study was to appraise existing alkenone-based climatic proxies in northern high latitudes. Unusually high percentages of the tetraunsaturated alkenone were measured in the polar waters of the East Greenland Current, with C37:4 of up to 77% in 80% of sea-ice cover. Values of percent C37:4 across the Nordic seas showed a strong association with water mass type. Analysis of coccoliths in filters indicated that calcified Emiliania huxleyi could not be discounted as the biological precursor of alkenones in all the water masses. A combined data set of 69 samples of POM revealed a stronger correlation of percent C37:4 to sea surface salinity (SSS; R2 = 0.72) than to sea surface temperature (SST; R2 = 0.50). Values of percent C37:4 in sea surface POM were much higher than those in surficial sediments of the northern North Atlantic. To explain the discrepancy in sedimentary and surface water column percent C37:4, we propose that the alkenone contents in surface sediments underlying arctic and polar waters are a combination of autochthonous and allochthonous inputs of alkenones. Our results show that percent C37:4 can be used to reconstruct the relative extension of arctic/polar water masses in the North Atlantic. However, the results prevent confirmation of percent C37:4 as a paleo-SSS proxy in the Nordic seas, given its multivariate nature in our data set and the decoupling between its range of values in surface waters and sediments.

Non-isoprenoidal intact polar lipids, isoprenoidal and non-isoprenoidal core lipids, isoprenoidal intact polar lipids of the Black Sea site GeoB15105 sampled during Meteor cruise M84/1 in February 2011

This PhD thesis focused on the analysis and application of microbial membrane lipids as biomarkers in marine sediments. Existing protocols for lipid extraction from marine sediments and biomass were modified. In addition, recent protocols based on high-performance liquid chromatography coupled to mass spectrometry (HPLC-MS) as well as state-of-the-art mass spectrometric analysis by quadrupole time-of-flight (MSqTOF) and the triple quadrupole (MSQQQ) mass spectrometer were used to investigate matrix effects and evaluate the reliability of quantitative analysis in marine environmental samples. The improved lipid extraction and quantification were used to analyze Black Sea water column and sediments samples to a depth of 8 meters from site GeoB 15105 taken during cruise M84/1 (DARCSEAS) with R/V Meteor to apply lipid analysis in benthic bio systems. With this component specific differentiation between planktonic and benthic lipid signature we assessed possible lipid sources. Here, this high detail lipid fingerprinting allowed us to observe changes in the head group and lipid core structures of the intact polar lipids according to the geochemical zonation.