Methane and sulfide fluxes in permanent anoxia: in situ studies at the Dvurechenskii mud volcano (Sorokin Trough, Black Sea)

The Dvurechenskii mud volcano (DMV), located in permanently anoxic waters at 2060 m depth (Sorokin Trough, Black Sea), was visited during the M72/2 cruise with the RV Meteor to investigate the methane and sulfide release from mud volcanoes into the Black Sea hydrosphere. We studied benthic fluxes of methane and sulfide, and the factors controlling transport, consumption and production of both compounds within the sediment. The pie shaped mud volcano showed temperature anomalies as well as solute and gas fluxes indicating high fluid flow at a small elevation north of the geographical center. The anaerobic oxidation of methane (AOM) coupled to sulfate reduction (SR) was excluded from this zone due to fluid-flow induced sulfate limitation and a fresh mud flow and consequently methane escaped into the water column with a rate of 0.46 mol/m**2/d. In the outer center of the mud volcano fluid flow and total methane flux were decreased, correlating with an increase in sulfate penetration into the sediment, and with higher SR and AOM rates. Here between 50-70% of the methane flux (0.07-0.1 mol/m**2/d) was consumed within the upper 10 cm of the sediment. Also at the edge of the mud volcano fluid flow and rates of methane and sulfate turnover were substantial. The overall amount of dissolved methane released from the mud volcano into the water column was significant with a discharge of 1.4x10**7 mol/yr. The DMV maintains also high areal rates of methane-fueled sulfide production of on average 0.05 mol/m**2/d. However, we concluded that sulfide and methane emission into the hydrosphere from deep water mud volcanoes does not significantly contribute to the sulfide and methane inventory of the Black Sea.

Aprubt climate change events in the Northeastern Atlantic Ocean

The western Iberian margin has been one of the key locations to study abrupt glacial climate change and associated interhemispheric linkages. The regional variability in the response to those events is being studied by combining a multitude of published and new records. Looking at the trend from Marine Isotope Stage (MIS) 10 to 2, the planktic foraminifer data, conform with the alkenone record of Martrat et al. [2007], shows that abrupt climate change events, especially the Heinrich events, became more frequent and their impacts in general stronger during the last glacial cycle. However, there were two older periods with strong impacts on the Atlantic meridional overturning circulation (AMOC): the Heinrich-type event associated with Termination (T) IV and the one occurring during MIS 8 (269 to 265 ka). During the Heinrich stadials of the last glacial cycle, the polar front reached the northern Iberian margin (ca. 41°N), while the arctic front was located in the vicinity of 39°N. During all the glacial periods studied, there existed a boundary at the latter latitude, either the arctic front during extreme cold events or the subarctic front during less strong coolings or warmer glacials. Along with these fronts sea surface temperatures (SST) increased southward by about 1°C per one degree of latitude leading to steep temperature gradients in the eastern North Atlantic and pointing to a close vicinity between subpolar and subtropical waters. The southern Iberian margin was always bathed by subtropical water masses - surface and/ or subsurface ones -, but there were periods when these waters also penetrated northward to 40.6°N. Glacial hydrographic conditions were similar during MIS 2 and 4, but much different during MIS 6. MIS 6 was a warmer glacial with the polar front being located further to the north allowing the subtropical surface and subsurface waters to reach at minimum as far north as 40.6°N and resulting in relative stable conditions on the southern margin. In the vertical structure, the Greenland-type climate oscillations during the last glacial cycle were recorded down to 2465 m during the Heinrich stadials, i.e. slightly deeper than in the western basin. This deeper boundary is related to the admixing of Mediterranean Outflow Water, which also explains the better ventilation of the intermediate-depth water column on the Iberian margin. This compilation revealed that latitudinal, longitudinal and vertical gradients existed in the waters along the Iberian margin, i.e. in a relative restricted area, but sufficient paleo-data exists now to validate regional climate models for abrupt climate change events in the northeastern North Atlantic Ocean.

Composition of organic carbon at ODP Site 128-798

Organic geochemical and sedimentological investigations have been performed on sediments from ODP Sites 798 and 799 in order to reconstruct the depositional environment in the Japan Sea through late Cenozoic times. The Miocene to Quaternary sediments from Site 798 (Oki Ridge) and Site 799 (Kita-Yamato Trough) are characterized by high organic carbon contents of up to 6%. The organic matter is mainly a mixture of marine and terrigenous material. The dominant factors controlling marine organic carbon enrichment in the sediments of Hole 798A are probably an increased surface-water productivity and/or an increased preservation rate of organic carbon under anoxic deep-water conditions. In lower Pliocene sediments at Site 798 and Miocene to Quaternary sediments at Site 799, rapid burial of organic matter in turbidites may have been important, too. Remarkable cycles of dark, laminated sediments distinctly enriched in (marine) organic carbon by up to 5% and light, bioturbated to homogeneous sediments with reduced organic carbon contents indicate dramatic short-term paleoenvironmental variation.

Aragonite distribution and preservation of sediment cores from the Brazilian Continental Slope

We present late Quaternary records of aragonite preservation determined for sediment cores recovered on the Brazilian Continental Slope (1790-2585 m water depth) where North Atlantic Deep Water (NADW) dominates at present. We have used various indirect dissolution proxies (carbonate content, aragonite/calcite contents, and sand percentages) as well as gastropodal abundances and fragmentation of Limacina inflata to determine the state of aragonite preservation. In addition, microscopic investigations of the dissolution susceptibility of three Limacina species yielded the Limacina Dissolution Index which correlates well with most of the other proxies. Excellent preservation of aragonite was found in the Holocene section, whereas aragonite dissolution gradually increases downcore. This general pattern is attributed to an overall increase in aragonite corrosiveness of pore waters. Overprinted on this early diagenetic trend are high-frequency fluctuations of aragonite preservation, which may be related to climatically induced variations of intermediate water masses.

Megnetic susceptibility of a subtropical South Atlantic transect

The Mid-Pleistocene transition (MPT) of the global climate system, initiated by a shift towards much larger northern hemisphere ice shields at around 920 ka and ending with predominance of 100 kyr ice age cyclicity since about 640 ka, is one of the fundamental enigmas in Quaternary climate evolution. Climate proxy records not exclusively linked to global ice volume are necessary to advance understanding of the MPT. Here we present a high-resolution Pleistocene magnetic susceptibility time series of 12 sediment cores from the subtropical South Atlantic essentially reflecting dissolution driven variations in carbonate accumulation controlled by changes in deep water circulation. In addition to characteristics known from delta18O records, the data sets reveal three remarkable features intimately related to the MPT: (1) an all-Pleistocene minimum of carbonate accumulation in the South Atlantic at 920 ka, (2) a MPT interim state of reduced carbonate deposition, indicating that the MPT period may have been a discrete state of the Pleistocene deep water circulation and climate system and (3) a terminal MPT event at around 540-530 ka documented in several peculiarities such as thick laminated layers of the giant diatom Ethmodiscus rex.

Neodymium isotopes in benthic foraminifera from the South Atlantic

Records of the past neodymium (Nd) isotope composition of the deep ocean can resolve ambiguities in the interpretation of other tracers. We present the first Nd isotope data for sedimentary benthic foraminifera. Comparison of the epsilon-Nd of core-top foraminifera from a depth transect on the Cape Basin side of the Walvis Ridge to published seawater data, and to the modern dissolved SiO2- epsilon-Nd trend of the deep Atlantic, suggests that benthic foraminifera represent a reliable archive of the deep water Nd isotope composition. Neodymium isotope values of benthic foraminifera from ODP Site 1264A (Angola Basin side of the Walvis Ridge) from the last 8 Ma agree with Fe-Mn oxide coatings from the same samples and are also broadly consistent with existing fish teeth data for the deep South Atlantic, yielding confidence in the preservation of the marine Nd isotope signal in all these archives. The marine origin of the Nd in the coatings is confirmed by their marine Sr isotope values. These important results allow application of the technique to down-core samples. The new epsilon-Nd datasets, along with ancillary Cd/Ca and Nd/Ca ratios from the same foraminiferal samples, are interpreted in the context of debates on the Neogene history of North Atlantic Deep Water (NADW) export to the South Atlantic. In general, the epsilon-Nd and delta13C records are closely correlated over the past 4.5 Ma. The Nd isotope data suggest strong NADW export from 8 to 5 Ma, consistent with one interpretation of published delta13C gradients. Where the epsilon-Nd record differs from the nutrient-based records, changes in the pre-formed delta13C or Cd/Ca of southern-derived deep water might account for the difference. Maximum NADW-export for the entire record is suggested by all proxies at 3.5-4 Ma. Chemical conditions from 3 to 1 Ma are totally different, showing, on average, the lowest NADW export of the record. Modern-day values again imply NADW export that is about as strong as at any stage over the past 8 Ma.

Stable isotope composition of Holocene benthic foraminifers from the Eastern Mediterranean Sea

Temporal and regional changes in paleoproductivity and paleoceanography in the eastern Mediterranean Sea during the past 12 kyr were reconstructed on the basis of the stable oxygen and carbon isotope composition of the epibenthic Planulina ariminensis and the shallow endobenthic Uvigerina mediterranea from three sediment cores of the Aegean Sea and Levantine Basin. The Younger Dryas is characterized by high d18O values, indicating enhanced salinities and low temperatures of deep water masses at all investigated sites. With the onset of the Holocene, d18O records show a continuous decrease towards the onset of sapropel S1 formation, mainly caused by a freshening and warming of surface waters at deep water formation sites. In the middle and late Holocene, the similarity of d18O values from the southern Aegean Sea and Levantine Basin suggests the influence of isotopically identical deep water masses. By contrast, slightly higher d18O values are observed the northern Aegean Sea, which probably point to lower temperatures of North Aegean deep waters. The epifaunal d13C records reveal clear changes in sources and residence times of eastern Mediterranean deep waters associated with period of S1 formation. Available data for the early and late phase of sapropel S1 formation and for the interruption around 8.2 kyr display drops by 0.5 and 1.5 per mil, indicating the slow-down of deep water circulation and enhanced riverine input of isotopically light dissolved inorganic carbon from terrestrial sources into the eastern Mediterranean Sea. The decrease in epifaunal d13C signals is particularly expressed in the southern Aegean Sea and Levantine Basin, while it is less pronounced in the northern Aegean Sea. This points to a strong reduction in deep water exchange rates in the southern areas, but the persistence of local deep water formation in the northern Aegean Sea. The d13C values of U. mediterranea records reveal temporal and regional differences in paleoproductivity during the past 12 kyr, with rather eutrophic and mesotrophic conditions in the North Aegean Sea and southeast Levantine Basin, respectively, while the South Aegean Sea is characterized by rather oligotrophic conditions. After S1 formation, increasing d13C values reflect a progressive decrease in surface water productivity in the eastern Mediterranean Sea during the middle and late Holocene. In the northern Aegean Sea, this time interval is marked by repetitive changes in organic matter fluxes documented by significant fluctuations in the d13C signal of U. mediterranea on millennial- to multi-centennial time scales. These fluctuations can be linked to short-term changes in river runoff driven by northern hemisphere climatic variability.

Chemical and physical oceanography on 131 CTD casts from METEOR cruise M59/2

The oceans absorb and store a significant portion of anthropogenic CO2 emissions, but large uncertainties remain in the quantification of this sink. An improved assessment of the present and future oceanic carbon sink is therefore necessary to provide recommendations for long-term global carbon cycle and climate policies. The formation of North Atlantic Deep Water (NADW) is a unique fast track for transporting anthropogenic CO2 into the ocean's interior, making the deep waters rich in anthropogenic carbon. Thus the Atlantic is presently estimated to hold 38% of the oceanic anthropogenic CO2 inventory, although its volume makes up only 25% of the world ocean. Here we analyze the inventory change of anthropogenic CO2 in the Atlantic between 1997 and 2003 and its relationship to NADW formation. For the whole region between 20°S and 65°N the inventory amounts to 32.5 ± 9.5 Petagram carbon (Pg C) in 1997 and increases up to 36.0 ± 10.5 Pg C in 2003. This result is quite similar to earlier studies. Moreover, the overall increase of anthropogenic carbon is in close agreement with the expected change due to rising atmospheric CO2 levels of 1.69% a?1. On the other hand, when considering the subpolar region only, the results demonstrate that the recent weakening in the formation of Labrador Sea Water, a component of NADW, has already led to a decrease of the anthropogenic carbon inventory in this water mass. As a consequence, the overall inventory for the total water column in the western subpolar North Atlantic increased only by 2% between 1997 and 2003, much less than the 11% that would be expected from the increase in atmospheric CO2 levels.

Age models of northern North Atlantic sediment cores

Benthic foraminiferal stable isotope records from four high-resolution sediment cores, forming a depth transect between 1237 m and 2303 m on the South Iceland Rise, have been used to reconstruct intermediate and deep water paleoceanographic changes in the northern North Atlantic during the last 21 ka (spanning Termination I and the Holocene). Typically, a sampling resolution of ~100 years is attained. Deglacial core chronologies are accurately tied to North Greenland Ice Core Project (NGRIP) ice core records through the correlation of tephra layers and changes in the percent abundance of Neogloboquadrina pachyderma (sinistral) with transitions in NGRIP. The evolution from the glacial mode of circulation to the present regime is punctuated by two periods with low benthic d13C and d18O values, which do not lie on glacial or Holocene water mass mixing lines. These periods correlate with the late Younger Dryas/Early Holocene (11.5-12.2 ka) and Heinrich Stadial 1 (14.7-16.8 ka) during which time freshwater input and sea-ice formation led to brine rejection both locally and as an overflow exported from the Nordic seas into the northern North Atlantic, as earlier reported by Meland et al. (2008). The export of brine with low ?13C values from the Nordic seas complicates traditional interpretations of low d13C values during the deglaciation as incursions of southern sourced water, although the spatial extent of this brine is uncertain. The records also reveal that the onset of the Younger Dryas was accompanied by an abrupt and transient (~200-300 year duration) decrease in the ventilation of the northern North Atlantic. During the Holocene, Iceland-Scotland Overflow Water only reached its modern flow strength and/or depth over the South Iceland Rise by 7-8 ka, in parallel with surface ocean reorganizations and a cessation in deglacial meltwater input to the North Atlantic.

Geochemistry of phosphate and glauconites of ODP Leg 128 samples

Glauconites and phosphates have been detected in almost all investigated samples at Sites 798 (uppermost Miocene or lower Pliocene to Pleistocene) and 799 (early middle Miocene to Pleistocene). Autochthonous occurrences appear in very minor quantities (generally below 0.2%) throughout the drilled sequences, whereas allochthonous accumulations are limited to the lower Pliocene or uppermost Miocene sequence at Site 798 (glauconites) and to the upper and middle Miocene sequence at Site 799 (upper and middle Miocene: glauconites; middle Miocene: phosphates). X-ray fluorescence, microprobe, and bulk chemical analyses indicate high variabilities in cations and anions and generally low oxide totals. This is probably related to the substitution of phosphate and fluoride aniors by hydroxide and carbonate anions in phosphates and to the depletion of iron, aluminum, and potassium cations and the enrichment in hydroxide and crystal water in glauconites. Gradients in pore-water contents of dissolved phosphate and fluoride at Sites 798 and 799 suggest a depth of phosphate precipitation between 30 and 50 mbsf, with fluoride as the limiting element for phosphate precipitation at Site 798. Phosphate and fluoride appear to be balanced at Site 799. Crude extrapolations indicate that the Japan-Sea sediments may have taken up approximately 7.2*10**10 g P total/yr during the Neogene and Pleistocene. This amount corresponds to approximately 0.3% of the estimated present-day global transfer of phosphorus into the sediments and suggests that the Japan Sea constitutes an average sink for this element. The two main carriers of phosphorus into the present Japan Sea are the Tshushima and the Liman currents, importing approximately 6.6*10**10 g P and 5.7*10**10 g P per year, respectively. Bulk chemical analyses suggest that at least 36% of P total in the sediments is organically bound phosphorus. This rather high value, which corresponds to the measured Japan-Sea deep-water P organic/P total ratios, probably reflects rapid transport of organic phosphorus into the depth of the Japan Sea.

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.