Particle camera and settling chamber measurements at site PC (GeoB11834-3) and SC (GeoB12914-4) off Cape Blanc/Mauritania

Particles sinking out of the euphotic zone are important vehicles of carbon export from the surface ocean. Most of the particles produce heavier aggregates by coagulating with each other before they sink. We implemented an aggregation model into the biogeochemical model of Regional Oceanic Modelling System (ROMS) to simulate the distribution of particles in the water column and their downward transport in the Northwest African upwelling region. Accompanying settling chamber, sediment trap and particle camera measurements provide data for model validation. In situ aggregate settling velocities measured by the settling chamber were around 55 m d**-1. Aggregate sizes recorded by the particle camera hardly exceeded 1 mm. The model is based on a continuous size spectrum of aggregates, characterised by the prognostic aggregate mass and aggregate number concentration. Phytoplankton and detritus make up the aggregation pool, which has an averaged, prognostic and size dependent sinking. Model experiments were performed with dense and porous approximations of aggregates with varying maximum aggregate size and stickiness as well as with the inclusion of a disaggregation term. Similar surface productivity in all experiments has been generated in order to find the best combination of parameters that produce measured deep water fluxes. Although the experiments failed to represent surface particle number spectra, in the deep water some of them gave very similar slope and spectrum range as the particle camera observations. Particle fluxes at the mesotrophic sediment trap site off Cape Blanc (CB) have been successfully reproduced by the porous experiment with disaggregation term when particle remineralisation rate was 0.2 d**-1. The aggregation-disaggregation model improves the prediction capability of the original biogeochemical model significantly by giving much better estimates of fluxes for both upper and lower trap. The results also point to the need for more studies to enhance our knowledge on particle decay and its variation and to the role that stickiness play in the distribution of vertical fluxes.

Superoxide decay rates during METEOR cruise M83/1

Superoxide is an important transient reactive oxygen species (ROS) in the ocean formed as an intermediate in the redox transformation of oxygen (O2) into hydrogen peroxide (H2O2) and vice versa. This highly reactive and very short-lived radical anion can be produced both via photochemical and biological processes in the ocean. In this paper we examine the decomposition rate of O2- throughout the water column, using new data collected in the Eastern Tropical North Atlantic (ETNA) Ocean. For this approach we applied a semi factorial experimental design, to identify and quantify the pathways of the major identified sinks in the ocean. In this work we occupied 6 stations, 2 on the West African continental shelf and 4 open ocean stations, including the CVOO time series site adjacent to Cape Verde. Our results indicate that in the surface ocean, impacted by Saharan aerosols and sediment resuspension, the main decay pathways for superoxide is via reactions with Mn(||) and organic matter.

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.

Marine barite in sediments of DSDP Site 54-424

The distribution of barite in sediments from D.S.D.P. sites 424 and 424A at the Galapagos hydrothermal mounds field is determined and the process of its formation is deduced. Barite in these deposits is associated with calcareous sediments and is completely absent from the hydrothermal material (manganese crusts and nontronite). Its concentrations tend to increase in the deeper sediments. Since manganese crusts contain significant amounts of Ba, a lack of barite in them is probably due to low concentrations of [SO4]2 in the sediment-seawater interface where they form. The formation of barite occurs within buried sediments, the interstitial waters of which are saturated with [SO4]2. The most probable source of [SO4]2- is the oxidation of H2S which is released from the hydrothermal fluids percolating upwards through the sediments. Although nontronite is formed within buried sediments the environmental conditions occurring during its formation (reducing) prevent barite formation. The association of barite with calcareous sediments is due to the release of Ba by calcareous microorganisms and/or to high concentrations of Ca in the pore waters which maintain a high pH and hence [SO4]2- is stable.

Pliocene sediment and silicon isotope record of ODP Site 145-882

Increases in the low-field mass-specific magnetic susceptibility (chi), dropstones and the terrigenous sediment component from Ocean Drilling Program (ODP) Site 882 (~45°N) have been interpreted to indicate a major onset of ice-rafting to the sub-Arctic northwest Pacific Ocean during marine isotope stage (MIS) G6 (from ~2.75 Ma). In contrast, studies of the terrigenous content of sediments cored downwind of ODP Site 882 indicate that dust and disseminated volcanic ash deposition in the sub-Arctic Pacific increased markedly during MIS G6. To investigate the relative contribution of dust, volcanic ash and ice rafting to the Pliocene chi increase, we present new high-resolution environmental magnetic and ice-rafted debris records from ODP Sites 882 and 885. Our results demonstrate that the chi increase at both sites across MIS G6 is predominantly controlled by a previously overlooked mixture of aeolian dust and volcanic ash. Our findings call into question the reliability of chi as a proxy for ice-rafting to the North Pacific. They also highlight a previously undocumented link between iron fertilisation and biogeochemical cycling in the North Pacific at a key stage during intensification of late Pliocene northern hemisphere glaciation.

Anaerobic oxidation of methane and sulphate reduction rates, hydrocarbons, sulphate and sulphide concentrations of sediment cores from the Larsen B embayment at the eastern site of the Antarctic Peninsula

First videographic indication of an Antarctic cold seep ecosystem was recently obtained from the collapsed Larsen B ice shelf, western Weddell Sea (Domack et al., 2005). Within the framework of the R/V Polarstern expedition ANTXXIII-8, we revisited this area for geochemical, microbiological and further videographical examinations. During two dives with ROV Cherokee (MARUM, Bremen), several bivalve shell agglomerations of the seep-associated, chemosynthetic clam Calyptogena sp. were found in the trough of the Crane and Evans glacier. The absence of living clam specimens indicates that the flux of sulphide and hence the seepage activity is diminished at present. This impression was further substantiated by our geochemical observations. Concentrations of thermogenic methane were moderately elevated with 2 µM in surface sediments of a clam patch, increasing up to 9 µM at a sediment depth of about 1 m in the bottom sections of the sediment cores. This correlated with a moderate decrease in sulphate from about 28 mM at the surface down to 23.4 mM, an increase in sulphide to up to 1.43 mM and elevated rates of the anaerobic oxidation of methane (AOM) of up to 600 pmol cm**-3 d**-1 at about 1 m below the seafloor. Molecular analyses indicate that methanotrophic archaea related to ANME-3 are the most likely candidates mediating AOM in sediments of the Larsen B seep.

Siliceous phytoplankton in Late Quaternary sediments of ODP Site 175-1077

Late Quaternary fluctuations in the intensity of Congo River freshwater load were reconstructed using three different proxies (marine and freshwater diatoms, and the delta18O record of Globigerinoides ruber) preserved in the sediments of Ocean Drilling Program (ODP) Site 1077, located at the northern rim of the Congo River fan (5°10'S, 10°26'E). An abrupt change in the diatom assemblage is evident at Termination II: a two- to four-fold increase in (a) the relative abundance of a marine planktonic diatom tolerant of low salinity conditions (Cyclotella litoralis), and (b) in the concentration of freshwater diatoms. The microfossil data suggest a change in the environmental conditions surrounding Site 1077 from predominantly marine to mixed marine/brackish/fresh. The delta18O record of the planktic foraminifera G. ruber (pink) revealed negative deviations from the global oxygen isotope signal since Termination II which occurred during warm stage 1 and substages 3.2, 5.1, 5.3, and 5.5. Comparison of the isotopic signal of ODP Site 1077 with the record from a pelagic location (core GeoB1041 at 3°48'S, 7°05'W) confirms these results. The construction of an artificial delta18O curve using alkenone-derived sea surface temperature (SST) data from a nearby core (GeoB1008 at 6°S, 10°E) allowed us to estimate salinity and temperature effects on the ODP Site 1077 isotopic signal. Although increased SSTs may account for lighter delta18O values during warmer periods, they do not explain the extremely light values documented in the sediments of Site 1077. We used the oxygen isotope difference (Delta delta18O) between our site and GeoB1041 as a proxy for freshwater input. A general trend in the Delta delta18O was observed, with more negative values since Termination II. In addition, conspicuous Delta delta18O negative pulses coincided with periods of northern hemisphere summer insolation maxima over the African continent, suggesting an increase in the freshwater discharge from the Congo River due to enhanced precipitation on the hinterland. Here we propose that the abrupt change in environmental conditions at Site 1077 since Termination II is a consequence of a major reorganization in the depositional environment of the Congo River delta. This reorganization involved sustained equatorward displacement of the Angola-Benguela Front causing a northward deflection of the Congo River plume thus moving plume waters further north than normal and over Site 1077.

Late Pliocene dinoflagellate cyst and diatom analysis from a high resolution sequence in DSDP Site 594, Chatham Rise, south west Pacific

A high resolution mixed carbonate and siliciclastic sequence from DSDP Site 594 contains a detailed record of climate change in the late Pliocene. The sequence can be accurately dated by the LAD of Nitzschia weaveri, the LAD of Thalassiosira insigna, the LAD of T. vulnifica and the LAD of T. kolbei diatom datums. Carbonate content and delta18O signatures provide added resolution and place the sequence between isotope stage 100 and 92. The sequence contains well-preserved and diverse dinoflagellate cyst floras. Use of principal component (PCA) and canonical correspondence analyses (CCA) identifies changes in the assemblages that principally reflect warming and cooling trends. Species association with warmer climates included Impagidinium patulum, I. paradoxum and I. sp. cf. paradoxum while those from cooler climates include Invertecysta tabulata and I. velorum. CCA is shown to be a valuable method of determining the past environmental preferences of extinct species such as I. tabulata.

137Cs and 90Sr depositions, and 137Cs/90Sr ratios of samples from the Kraton-3 underground nuclear explosion site, Russia

Strontium-90 activity concentrations in surface soils and areal deposition densities have been studied at a site contaminated by an accidental release to atmosphere from the underground nuclear explosion 'Kraton-3' conducted near the Polar Circle (65.9°N, 112.3°E) within the territory of the former USSR in 1978. In 2001-2002, the ground surface contamination at 14 plots studied ranged from 20 to 15000 kBq/m**2, which significantly exceeds the value of 0.44 kBq/m**2 deduced for three background plots. The zone with substantial radiostrontium contamination extends, at least, 2.5 km in a north-easterly direction from the borehole. The average 137Cs/90Sr ratio in the ground contamination originated from the 'Kraton-3' fallout was estimated to be 0.55, which is significantly different from the ratio of 2.05 evaluated for background plots contaminated mostly from global fallout. Although vertical migration of 90Sr in all undisturbed soil profiles studied is more rapid than that for 137Cs, the depth of percolation of both radionuclides into the ground is mostly limited to the top 10-20 cm, which may be explained, primarily, by permafrost conditions. The horizontal migration rate of radiostrontium in the aqueous phase exceeds the radiocaesium migration rate by many times. This phenomenon seems to be a reason for the significant enrichment of the soil surface layers by radiostrontium at some sites, with variations occurring in accordance with small-scale irregularities of landscape.

Organic matter and sediment properties of samples from site GeoB15105 from the Black Sea

Dissolved organic matter (DOM) in marine sediments is a complex mixture of thousands of individual constituents that participate in biogeochemical reactions and serve as substrates for benthic microbes. Knowledge of the molecular composition of DOM is a prerequisite for a comprehensive understanding of the biogeochemical processes in sediments. In this study, interstitial water DOM was extracted with Rhizon samplers from a sediment core from the Black Sea and compared to the corresponding water-extractable organic matter fraction (<0.4 µm) obtained by Soxhlet extraction, which mobilizes labile particulate organic matter and DOM. After solid phase extraction (SPE) of DOM, samples were analyzed for the molecular composition by Fourier Transform Ion-Cyclotron Resonance Mass Spectrometry (FT-ICR MS) with electrospray ionization in negative ion mode. The average SPE extraction yield of the dissolved organic carbon (DOC) in interstitial water was 63%, whereas less than 30% of the DOC in Soxhlet-extracted organic matter was recovered. Nevertheless, Soxhlet extraction yielded up to 4.35% of the total sedimentary organic carbon, which is more than 30-times the organic carbon content of the interstitial water. While interstitial water DOM consisted primarily of carbon-, hydrogen- and oxygen-bearing compounds, Soxhlet extracts yielded more complex FT-ICR mass spectra with more peaks and higher abundances of nitrogen- and sulfur-bearing compounds. The molecular composition of both sample types was affected by the geochemical conditions in the sediment; elevated concentrations of HS- promoted the early diagenetic sulfurization of organic matter. The Soxhlet extracts from shallow sediment contained specific three- and four-nitrogen-bearing molecular formulas that were also detected in bacterial cell extracts and presumably represent proteinaceous molecules. These compounds decreased with increasing sediment depth while one- and two-nitrogen-bearing molecules increased, resulting in a higher similarity of both sample types in the deep sediment. In summary, Soxhlet extraction of sediments accessed a larger and more complex pool of organic matter than present in interstitial water DOM.