ALBERT

Beschreibung: The Weddell Sea and the associated Filchner-Rønne Ice Shelf constitute key regions for global bottomwater production today. However, little is known about bottom-water production under different climate and icesheet conditions. Therefore, we studied core PS1795, which consists primarily of fine-grained siliciclastic varves that were deposited on contourite ridges in the southeastern Weddell Sea during the Last Glacial Maximum (LGM). We conducted high-resolution X-ray fluorescence (XRF) analysis and grain-size measurements with the RADIUS tool (Seelos and Sirocko, 2005, doi:10.1111/j.1365-3091.2005.00715.x) using thin sections to characterize the two seasonal components of the varves at sub-mm resolution to distinguish the seasonal components of the varves. Bright layers contain coarser grains that can mainly be identified as quartz in the medium-to-coarse silt grain size. They also contain higher amounts of Si, Zr, Ca, and Sr, as well as more ice-rafted debris (IRD). Dark layers, on the other hand, contain finer particles such as mica and clay minerals from the chlorite and illite groups. In addition, Fe, Ti, Rb, and K are elevated. Based on these findings as well as on previous analyses on neighbouring cores, we propose a model of enhanced thermohaline convection in front of a grounded ice sheet that is supported by seasonally variable coastal polynya activity during the LGM. Accordingly, katabatic (i.e. offshore blowing) winds removed sea ice from the ice edge, leading to coastal polynya formation. We suggest that glacial processes were similar to today with stronger katabatic winds and enhanced coastal polynya activity during the winter season. Under these conditions, lighter coarser-grained layers are likely glacial winter deposits, when brine rejection was increased, leading to enhanced bottom-water formation and increased sediment transport. Vice versa, darker finer-grained layers were then deposited during less windier season, mainly during summer, when coastal polynya activity was likely reduced.

Beschreibung: Vodyanitskii mud volcano is located at a depth of about 2070 m in the Sorokin Trough, Black sea. It is a 500-m wide and 20-m high cone surrounded by a depression, which is typical of many mud volcanoes in the Black Sea. 75 kHz sidescan sonar show different generations of mud flows that include mud breccia, authigenic carbonates, and gas hydrates that were sampled by gravity coring. The fluids that flow through or erupt with the mud are enriched in chloride (up to 650 mmol L**-1 at 150-cm sediment depth) suggesting a deep source, which is similar to the fluids of the close-by Dvurechenskii mud volcano. Direct observation with the remotely operated vehicle Quest revealed gas bubbles emanating at two distinct sites at the crest of the mud volcano, which confirms earlier observations of bubble-induced hydroacoustic anomalies in echosounder records. The sediments at the main bubble emission site show a thermal anomaly with temperatures at 60 cm sediment depth that were 0.9 °C warmer than the bottom water. Chemical and isotopic analyses of the emanated gas revealed that it consisted primarily of methane (99.8%) and was of microbial origin (dD-CH4 = -170.8 per mil (SMOW), d13C-CH4 = -61.0 per mil (V-PDB), d13C-C2H6 = -44.0 per mil (V-PDB)). The gas flux was estimated using the video observations of the ROV. Assuming that the flux is constant with time, about 0.9 ± 0.5 x 10**6 mol of methane is released every year. This value is of the same order-of-magnitude as reported fluxes of dissolved methane released with pore water at other mud volcanoes. This suggests that bubble emanation is a significant pathway transporting methane from the sediments into the water column.

Beschreibung: Present day hydrographic conditions along the western Iberian margin are characterized by seasonal upwelling with filaments that can penetrate more than 200 km into the open ocean and constitute areas of cold and highly productive waters. In order to investigate spatial and temporal gradients in temperature and productivity conditions during the last 150 ky, high-resolution proxy records were generated in 3 cores (SU92-03, MD95-2040, MD95-2042), located along the Iberian coast between 43°12'N and 37°48'N and forming a N-S profile. In all cores, planktonic foraminifera census counts are used to reconstruct summer sea surface temperature (SSTsu) and export productivity (Pexpsu) using the modern analog technique SIMMAX 28. SSTsu and Pexpsu values similar to the present are observed throughout the Holocene and MIS 5e periods for each site, respectively, indicating fairly stable conditions equivalent to the modern ones. On glacial/interglacial timescales, SSTsu increases by 2-3 °C from the northern to southernmost site. Pexpsu, on the other hand, shows a decrease of 30-40 gC/m**2/yr from North to South at present time and during interglacial periods, and no significant variation (90-100 gC/m**2/yr) during glacial periods. The northernmost core SU92-03 reveals the coldest conditions with records more similar to MD95-2040 than to MD95-2042, the later of which is, as at present, more affected by subtropical waters. Core SU92-03 shows higher interglacial productivity similar to open ocean mid- to high latitude sites, while the other two cores monitor higher glacial productivity conform with other upwelling sites off NW Africa. A boundary between differences in glacial/interglacial productivity appears to be present in our study between 43°12'N and 40°35'N. Especially north of 40°N, coldest SSTsu and lowest Pexpsu are found during Heinrich events (H)1-H8 and H10-H11. In contrast, lowest Pexpsu do not coincide with these events at site MD95-2042, but appear to be related to the presence of relatively warm and nutrient-poor subtropical Eastern North Atlantic Central Water advected with the Azores Current.

Beschreibung: Authigenic carbonates associated with cold seeps provide valuable archives of changes in the long-term seepage activity. To investigate the role of shallow-buried hydrates on the seepage strength and fluid composition we analysed methane-derived carbonate precipitates from a high-flux hydrocarbon seepage area ("Batumi seep area") located on the south-eastern Black Sea slope in ca. 850 m. In a novel approach, we combined computerized X-ray tomography (CT) with mineralogical and isotope geochemical methods to get additional insights into the three-dimensional internal structure of the carbonate build-ups. X-ray diffractometry revealed the presence of two different authigenic carbonate phases, i.e. pure aragonitic rims associated with vital microbial mats and high-Mg calcite cementing the hemipelagic sediment. As indicated by the CT images, the initial sediment has been strongly deformed, first plastic then brittle, leading to brecciation of the progressively cemented sediment. The aragonitic rims on the other hand, represent a presumably recent carbonate growth phase since they cover the already deformed sediment. The stable oxygen isotope signature indicates that the high-Mg calcite cement incorporated pore water mixed with substantial hydrate water amounts. This points at a dominant role of high gas/fluid flux from decomposing gas hydrates leading to the deformation and cementation of the overlying sediment. In contrast, the aragonitic rims do not show an influence of 18O-enriched hydrate water. The differences in d18O between the presumably recent aragonite precipitates and the older high-Mg cements suggest that periods of hydrate dissociation and vigorous fluid discharge alternated with times of hydrate stability and moderate fluid flow. These results indicate that shallow-buried gas hydrates are prone to episodic decomposition with associated vigorous fluid flow. This might have a profound impact on the seafloor morphology resulting e.g. in the formation of carbonate pavements and pockmark-like structures but might also affect the local carbon cycle.

Beschreibung: Detailed knowledge of the extent of post-genetic modifications affecting shallow submarine hydrocarbons fueled from the deep subsurface is fundamental for evaluating source and reservoir properties. We investigated gases from a submarine high-flux seepage site in the anoxic Eastern Black Sea in order to elucidate molecular and isotopic alterations of low-molecular-weight hydrocarbons (LMWHC) associated with upward migration through the sediment and precipitation of shallow gas hydrates. For this, near-surface sediment pressure cores and free gas venting from the seafloor were collected using autoclave technology at the Batumi seep area at 845 m water depth within the gas hydrate stability zone. Vent gas, gas from pressure core degassing, and from hydrate dissociation were strongly dominated by methane (〉99.85 mol.% of Sum[C1-C4, CO2]). Molecular ratios of LMWHC (C1/[C2 + C3] 〉 1000) and stable isotopic compositions of methane (d13C = -53.5 per mill V-PDB; D/H around -175 per mill SMOW) indicated predominant microbial methane formation. C1/C2+ ratios and stable isotopic compositions of LMWHC distinguished three gas types prevailing in the seepage area. Vent gas discharged into bottom waters was depleted in methane by 〉0.03 mol.% (Sum[C1-C4, CO2]) relative to the other gas types and the virtual lack of 14C-CH4 indicated a negligible input of methane from degradation of fresh organic matter. Of all gas types analyzed, vent gas was least affected by molecular fractionation, thus, its origin from the deep subsurface rather than from decomposing hydrates in near-surface sediments is likely. As a result of the anaerobic oxidation of methane, LMWHC in pressure cores in top sediments included smaller methane fractions [0.03 mol.% Sum(C1-C4, CO2)] than gas released from pressure cores of more deeply buried sediments, where the fraction of methane was maximal due to its preferential incorporation in hydrate lattices. No indications for stable carbon isotopic fractionations of methane during hydrate crystallization from vent gas were found. Enrichments of 14C-CH4 (1.4 pMC) in short cores relative to lower abundances (max. 0.6 pMC) in gas from long cores and gas hydrates substantiates recent methanogenesis utilizing modern organic matter deposited in top sediments of this high-flux hydrocarbon seep area.

Beschreibung: The Hakon Mosby Mud Volcano is a highly active methane seep hosting different chemosynthetic communities such as thiotrophic bacterial mats and siboglinid tubeworm assemblages. This study focuses on in situ measurements of methane fluxes to and from these different habitats, in comparison to benthic methane and oxygen consumption rates. By quantifying in situ oxygen, methane, and sulfide fluxes in different habitats, a spatial budget covering areas of 10-1000 -m diameter was established. The range of dissolved methane efflux (770-2 mmol m-2 d-1) from the center to the outer rim was associated with a decrease in temperature gradients from 46°C to 〈 1°C m-1, indicating that spatial variations in fluid flow control the distribution of benthic habitats and activities. Accordingly, total oxygen uptake (TOU) varied between the different habitats by one order of magnitude from 15 mmol m-2 d-1 to 161 mmol m-2 d-1. High fluid flow rates appeared to suppress benthic activities by limiting the availability of electron acceptors. Accordingly, the highest TOU was associated with the lowest fluid flow and methane efflux. This was most likely due to the aerobic oxidation of methane, which may be more relevant as a sink for methane as previously considered in submarine ecosystems.

Beschreibung: Gas hydrate samples from various locations in the Gulf of Mexico (GOM) differ considerably in their microstructure. Distinct microstructure characteristics coincide with discrete crystallographic structures, gas compositions and calculated thermodynamic stabilities. The crystallographic structures were established by X-ray diffraction, using both conventional X-ray sources and high-energy synchrotron radiation. The microstructures were examined by cryo-stage Field-Emission Scanning Electron Microscopy (FE-SEM). Good sample preservation was warranted by the low ice fractions shown from quantitative phase analyses. Gas hydrate structure II samples from the Green Canyon in the northern GOM had methane concentrations of 70-80% and up to 30% of C2-C5 of measured hydrocarbons. Hydrocarbons in the crystallographic structure I hydrate from the Chapopote asphalt volcano in the southern GOM was comprised of more than 98% methane. Fairly different microstructures were identified for those different hydrates: Pores measuring 200-400 nm in diameter were present in structure I gas hydrate samples; no such pores but dense crystal surfaces instead were discovered in structure II gas hydrate. The stability of the hydrate samples is discussed regarding gas composition, crystallographic structure and microstructure. Electron microscopic observations showed evidence of gas hydrate and liquid oil co-occurrence on a micrometer scale. That demonstrates that oil has direct contact to gas hydrates when it diffuses through a hydrate matrix.

Beschreibung: Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.

Beschreibung: The loss of Arctic sea ice has accelerated in recent years. With the decline in sea ice cover, the Arctic Ocean biogeochemistry is undergoing unprecedented change. A key question about the changing Arctic Ocean biogeochemistry is concerning the impact of the shrinking sea ice cover on the particulate organic carbon (POC) export from the upper Arctic Ocean. Thus far, there are still very few direct measurements of POC export in the permanently ice-covered central Arctic Ocean. A further issue is that the magnitude of the POC export so far documented in this region remains controversial. During the ARK-XXII/2 expedition to the Arctic Ocean from 28 July to 7 October in 2007, we conducted a high-resolution study of POC export using 234Th/238U disequilibrium. Depth profiles of total 234Th in the upper 200 m were collected at 36 stations in the central Arctic Ocean and its adjacent seas, i.e., the Barents Sea, the Kara Sea and the Laptev Sea. Samples were processed using a small-volume MnO2 coprecipitation method with addition of a yield tracer, which resulted in one of the most precise 234Th data sets ever collected. Thorium-234 deficit with respect to 238U was found to be evident throughout the upper 100 m over the Arctic shelves. In comparison, 234Th deficit was confined to the upper 25 m in the central Arctic Ocean. Below 25 m, secular equilibrium was approached between 234Th and 238U. The observed 234Th deficit was generally associated with enhanced total chlorophyll concentrations, indicating that in situ production and export of biogenic particles are the main mechanism for 234Th removal in the Arctic Ocean. Thorium-234-derived POC fluxes were determined with a steady state model and pump-normalized POC/234Th ratios on total suspended particles collected at 100 m. Results showed enhanced POC export over the Arctic shelves. On average, POC export fluxes over the various Arctic shelves were 2.7 ± 1.7 mmol m**-2 d**-1 (the Barents Sea), 0.5 ± 0.8 mmol m**-2 d**-1 (the Kara Sea), and 2.9 ± 1.8 mmol m**-2 d**-1 (the Laptev Sea) respectively. In comparison, the central Arctic Ocean was characterized by the lowest POC export flux ever reported, 0.2 ± 1.0 mmol m**-2 d**-1 (1 standard deviation, n = 26). This value is very low compared to prior estimates and is also much lower than the POC export fluxes reported in other oligotrophic oceans. A ThE ratio (234Th-derived POC export/primary production) of 〈6% in the central Arctic Ocean was estimated using the historical measurements of primary production. The low ThE ratio indicates that like other oligotrophic regimes, the central Arctic Ocean is characterized by low POC export relative to primary production, i.e., a tightly coupled food web. Our study strongly suggests that the current role of the central Arctic Ocean in C sequestration is still very limited. Meanwhile, this role might be altered because of global warming and future decline in sea ice cover.