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.

Late Quaternary siliciclastic/carbonate sedimentation in the Cabricorn Channel

A model is presented for hemipelagic siliciclastic and carbonate sedimentation during the last glacial-interglacial cycle in the Capricorn Channel, southern Great Barrier Reef (GBR). Stable isotope ratios, grainsize, carbonate content and mineralogy were analysed for seven cores in a depth transect from 166 to 2892 m below sea level (mbsl). Results show variations in the flux of terrigenous, neritic and pelagic sediments to the continental slope over the last sea level cycle. During the glacial lowstand terrigenous sediment influenced all the cores down to 2000 mbsl. The percentages of quartz and feldspar in the cores decreased with water depth, while the percentage of clay increased. X-ray diffraction analysis of the glacial lowstand clay mineralogy suggests that the siliciclastic sediment was primarily sourced from the Fitzroy River, which debouched directly into the northwest sector of the Capricorn Channel at this time. The cores also show a decrease in pelagic calcite and an increase in aragonite and high magnesium calcite (HMC) during the glacial. The influx of HMC and aragonite is most likely from reworking of coral reefs exposed on the continental shelf during the glacial, and also from HMC ooids precipitated at the head of the Capricorn Channel at this time. Mass accumulation rates (MARs) are high (13.5 g/cm**/kyr) during the glacial and peak at ~20 g/cm** 3/kyr in the early transgression (16-14 ka BP). MARs then decline with further sea level rise as the Fitzroy River mouth retreats from the edge of the continental shelf after 13.5 ka BP. MARs remain low (4 g/cm**3/kyr) throughout the Holocene highstand. Data for the Holocene highstand indicate there is a reduction in siliciclastic influx to the Capricorn Channel with little quartz and feldspar below 350 mbsl. However, fine-grained fluvial sediments, presumably from the Fitzroy River, were still accumulating on the mid slope down to 2000 mbsl. The proportion of pelagic calcite in the core tops increases with water depth, while HMC decreases, and is present only in trace amounts in cores below 1500 mbsl. The difference in the percentage of HMC in the deeper cores between the glacial and Holocene may reflect differences in supply or deepening of the HMC lysocline during the glacial. Sediment accumulation rates also vary between cores in the Capricorn Channel and do not show the expected exponential decrease with depth. This may be due to intermediate or deep water currents reworking the sediments. It is also possible that present bathymetry data are too sparse to detect the potential role that submarine channels may play in the distribution and accumulation of sediments. Comparison of the Capricorn Channel MARs with those for other mixed carbonate/siliciclastic provinces from the northeast margin of Australia indicates that peak MARs in the early transgression in the Capricorn Channel precede those from the central GBR and south of Fraser Island. The difference in the timing of the carbonate and siliciclastic MAR peaks along the northeast margin is primarily related to differences in the physiography and climate of the provinces. The only common trend in the MARs from the northeast margin of Australia is the near synchronicity of the carbonate and siliciclastic MAR peaks in individual sediment cores, which supports a coeval sedimentation model.

Granulometry and Bulk Geochemistry of Nearshore Sediments, Herschel Island, Yukon Territory, Canada

This dataset contains the results of granulometric and bulk geochemical analyses of Van Veen surface samples obtained by the Alfred Wegener Institute (AWI) in the course of the 2012 and 2013 summer field seasons. The sampling was performed along transects in depths generally <13 m, to a distance of about <5 km off Herschel Island. In 2012, 75 samples in Pauline Cove and in the vicinity of Simpson Point were obtained. Sample collection was expanded in 2013, on transects established the previous year, with additional locations in Tetris Bay and Workboat Passage. Samples consisted of approximately 100 g of the top 3-6 cm of sediment, and were frozen in the field and freeze dried at the AWI before undergoing analytical procedures. Sample locations were recorded with the onboard global positioning system (GPS) unit. Grain size distributions in our study were obtained using laser diffractometry at the AWI (Beckman Coulter LS200) on the <1 mm fraction of samples oxidized with 30% H2O2 until effervescence ceased to remove organics. Some samples were also sieved using a sieve stack with 1 phi intervals. GRADISTAT (Blott and Pye, 2001) was used to calculate graphical grain size statistics (Folk and Ward, 1957). Grain diameters were logarithmically transformed to phi values, calculated as phi=-log2d, where d is the grain diameter in millimeters (Blott and Pye, 2001; Krumbein, 1934). Freeze dried samples were ground and ground using an Elemetar Vario EL III carbon-nitrogen-sulphur analyzer at the AWI to measure total carbon (TC) and total nitrogen (TN). Tungsten oxide was added to the samples as a catalyst to the pyrolysis. Following this analysis, total organic carbon (TOC) was determined using an Elementar VarioMax. Stable carbon isotope ratios of 13C/12C of 118 samples were determined on a DELTAplusXL mass spectrometer (ThermoFisher Scientific, Bremen) at the German Research Centre for Geosciences (GFZ) in Potsdam, Germany . An additional analysis on 69 samples was carried out at the University of Hamburg with an isotope ratio mass spectrometer (Delta V, Thermo Scientific, Germany) coupled to an elemental analyzer (Flash 2000, Thermo Scientific, Germany). Prior to analysis, soil samples were treated with phosphoric acid (43%) to release inorganic carbon. Values are expressed relative to Vienna Peedee belemnite (VPDB) using external standards (USGS40, -26.4 per mil VPDB and IVA soil 33802153, -27.5 per mil VPDB).

A foraminiferal d18O record of sediment core GT90-3 covering the last 2,200 years

For many years the Torino Cosmogeophysics group has been studying sediment cores drilled from the Gallipoli Terrace in the Gulf of Taranto (Ionian Sea) and deposited in the last millennia. The gravity core GT90-3, in which the 18O series was measured, was drilled from the Gallipoli Terrace in the Gulf of Taranto (Ionian Sea) at 39°45'53''N, 17°53'33''E. It was extracted at a depth of 178 m and its length is 3.57 m. Thanks to its geographical location, the Gallipoli Terrace is a favourable site for climatic studies based on marine sediments, because of its closeness to the volcanically active Campanian area, a region that is unique in the world for its detailed historical documentation of volcanic eruptions. Tephra layers corresponding to historical eruptions were identified along the cores, thus allowing for accurate dating and determination of the sedimentation rate. The measurements performed in different cores from the same area showed that the sedimentation rate is uniform across the whole Gallipoli Terrace. We measured the oxygen isotope composition d18O of planktonic foraminifera. These measurements provided a high-resolution 2,200-year-long record. We sampled the core using a spacing of 2.5 mm corresponding to 3.87 years. Each sample of sediment (5 g) was soaked in 5% calgon solution overnight, then treated in 10% H2O2 to remove any residual organic material. Subsequently it was washed with a distilled-water jet through a sieve with a 150 µm mesh. The fraction > 150 µm was kept and oven-dried at 5°C. The planktonic foraminifera Globigerinoides ruber were picked out of the samples under a microscope. For each sample, 20-30 specimens were selected from the fraction comprised between 150 µm and 300 µm. The use of a relatively large number of specimens for each sample reduces the isotopic variability of individual organisms, giving a more representative d18O value. The stable isotope measurements were performed using a VG-PRISM mass spectrometer fitted with an automated ISO-CARB preparation device. Analytical precision based on internal standards was better than 0.1 per mil. Calibration of the mass spectrometer to VPDB scale was done using NBS19 and NBS18 carbonate standards. The strategic location of the drilling area makes this record a unique tool for climate and oceanographic studies of the Central Mediterranean.

Dynamics of halocarbons in coastal surface waters during short term mesocosm experiments

The aim of the present study was to evaluate the influence of different light quality, especially ultraviolet radiation (UVR), on the dynamics of volatile halogenated organic compounds (VHOCs) at the sea surface. Short term experiments were conducted with floating gas-tight mesocosms of different optical qualities. Six halocarbons (CH3I, CHCl3, CH2Br2, CH2ClI, CHBr3 and CH2I2), known to be produced by phytoplankton, together with a variety of biological and environmental variables were measured in the coastal southern Baltic Sea and in the Raunefjord (North Sea). These experiments showed that ambient levels of UVR have no significant influence on VHOC dynamics in the natural systems. We attribute it to the low radiation doses that phytoplankton cells receive in a normal turbulent surface mixed layer. The VHOC concentrations were influenced by their production and removal processes, but they were not correlated with biological or environmental parameters investigated. Diatoms were most likely the dominant biogenic source of VHOCs in the Baltic Sea experiment, whereas in the Raunefjord experiment macroalgae probably contributed strongly to the production of VHOCs. The variable stable carbon isotope signatures (d13C values) of bromoform (CHBr3) also indicate that different autotrophic organisms were responsible for CHBr3 production in the two coastal environments. In the Raunefjord, despite strong daily variations in CHBr3 concentration, the carbon isotopic ratio was fairly stable with a mean value of -26 per mil. During the declining spring phytoplankton bloom in the Baltic Sea, the d13C values of CHBr3 were enriched in 13C and showed noticeable diurnal changes (-12 per mil ± 4). These results show that isotope signature analysis is a useful tool to study both the origin and dynamics of VHOCs in natural systems.

Planktonic foraminifera of sediment trap samples

Biweekly sediment trap samples and concurrent hydrographic measurements collected between March 2005 and October 2008 from the Cariaco Basin, Venezuela, are used to assess the relationship between [CO3]2- and the area densities (ho A) of two species of planktonic foraminifera (Globigerinoides ruber (pink) and Globigerinoides sacculifer). Calcification temperatures were calculated for each sample using species-appropriate oxygen isotope (d18O) temperature equations that were then compared to monthly temperature profiles taken at the study site in order to determine calcification depth. Ambient [CO3]2- was determined for these calcification depths using alkalinity, pH, temperature, salinity, and nutrient concentration measurements taken during monthly hydrographic cruises. The rho A, which is representative of calcification efficiency, is determined by dividing individual foraminiferal shell weights (±0.43 µg) by their associated silhouette areas and taking the sample average. The results of this study show a strong correlation between rho A and ambient [CO3]2- for both G. ruber and G. sacculifer (R**2 = 0.89 and 0.86, respectively), confirming that [CO3]2- has a pronounced effect on the calcification of these species. Though the rho A for both species reveal a highly significant (p < 0.001) relationship with ambient [CO3]2-, linear regression reveals that the extent to which [CO3]2- influences foraminiferal calcification is species specific. Hierarchical regression analyses indicate that other environmental parameters (temperature and [PO4]3-) do not confound the use of G. ruber and G. sacculifer rho A as a predictor for [CO3]2-. This study suggests that G. ruber and G. sacculifer rho A can be used as reliable proxies for past surface ocean [CO3]2?-

Benthic and planktic foraminiferal stable isotope record and coccolith abundance spanning the last 500,000 years of ODP Hole 121-758C

The Indian Summer Monsoon (ISM) is an inter-hemispheric and highly variable ocean-atmosphere-land interaction that directly affects the densely populated Indian subcontinent. Here, we present new records of palaeoceanographic variability that span the last 500,000 years from the eastern equatorial Indian Ocean, a relatively under-sampled area of ISM influence. We have generated carbon and oxygen stable isotope records from three foraminiferal species from Ocean Drilling Program Site 758 (5°N, 90°E) to investigate the oceanographic history of this region. We interpret our resultant Dd18O (surface-thermocline) record of upper water-column stratification in the context of past ISM variability, and compare orbital phase relationships in our Site 758 data to other climate and monsoon proxies in the region. Results suggest that upper water-column stratification at Site 758, which is dominated by variance at precession and half-precession frequencies (23, 19 and 11 ka), is forced by both local (5°N) insolation and ISM winds. In the precession (23 ka) band, stratification minima at Site 758 lag northern hemisphere summer insolation maxima (precession minima) by 9 ka, which is consistent with Arabian Sea ISM phase estimates and suggests a common wind forcing in both regions. This phase implicates a strong sensitivity to both ice volume and southern hemisphere insolation forcing via latent heat export from the southern subtropical Indian Ocean. Additionally, we find evidence of possible overprinting of millennial-scale events during glacial terminations in our stratification record, which suggests an influence of remote abrupt climate events on ISM dynamics.

Stable isotope record, carbonate and organic carbon content of the Miocene section of IODP Site 321-U1337

The Miocene Climatic Optimum (~17-14.7 Ma) represents one of several major interruptions in the long-term cooling trend of the past 50 million years. To date, the processes driving high-amplitude climate variability and sustaining global warmth during this remarkable interval remain highly enigmatic. We present high-resolution benthic foraminiferal and bulk carbonate stable isotope records in an exceptional, continuous, carbonate-rich sedimentary archive (Integrated Ocean Drilling Program Site U1337, eastern equatorial Pacific Ocean), which offer a new view of climate evolution over the onset of the Climatic Optimum. A sharp decline in d18O and d13C at ~16.9 Ma, contemporaneous with a massive increase in carbonate dissolution, demonstrates that abrupt warming was coupled to an intense perturbation of the carbon cycle. The rapid recovery in d13C at ~16.7 Ma, ~200 k.y. after the beginning of the MCO, marks the onset of the first carbon isotope maximum within the long-lasting "Monterey Excursion". These results lend support to the notion that atmospheric pCO2 variations drove profound changes in the global carbon reservoir through the Climatic Optimum, implying a delicate balance between changing CO2 fluxes, rates of silicate weathering and global carbon sequestration. Comparison with a high-resolution d13C record spanning the onset of the Cretaceous Oceanic Anoxic Event 1a (~120 Ma ago) reveals common forcing factors and climatic responses, providing a long-term perspective to understand climate-carbon cycle feedbacks during warmer periods of Earth's climate with markedly different atmospheric CO2 concentrations.

Benthic foraminiferal assemblages and epifaunal isotope record of the Agulhas Plateau

Benthic foraminiferal assemblages and the carbon isotope composition of the epifaunal benthic foraminifera Epistominella exigua and Fontbotia wuellerstorfi have been investigated along core MD02-2589 located at the southern Agulhas Plateau (41°26.03'S, 25°15.30'E, 2660 m water depth). This study aims to evaluate changes in the benthic paleoenvironment and its influence on benthic d13C with a notable focus on E. exigua, a species associated with phytodetritus deposits and poorly studied in isotope paleoceanographic reconstructions. The benthic foraminiferal assemblages (>63 µm) show large fluctuations in species composition suggesting significant changes in the pattern of ocean surface productivity conceivably related to migrations of the Subtropical Convergence (STC) and Subantarctic Front (SAF). Low to moderate seasonality and relatively higher food supply to the seafloor are indicated during glacial marine isotope stages (MIS) 6, 4, and 2 and during MIS 3, probably associated with the northward migration of the SAF and confluence with the more stationary STC above the southern flank of the Agulhas Plateau. The lowest organic carbon supply to the seafloor is indicated from late MIS 5b to MIS 4 as a consequence of increased influence of the Agulhas Front (AF) and/or weakening of the influence of the STC over the region. Episodic delivery of fresh organic matter, similar to modern conditions at the core location, is indicated during MIS 5c-MIS 5e and at Termination I. Comparison of this paleoenvironmental information with the paired d13C records of E. exigua and F. wuellerstorfi suggests that organic carbon offsets d13C of E. exigua from ambient bottom water d13CDIC, while its d13C amplitude, on glacial-interglacial timescales, does not seem affected by changes of organic carbon supply to the seafloor. This suggests that this species calcifies preferentially during the short time span of the year when productivity peaks and phytodetritus is delivered to the seafloor. Therefore E. exigua, while offset from d13CDIC, potentially more faithfully records the amplitude of ambient bottom water d13CDIC changes than F. wuellerstorfi, notably in settings such as the Southern Ocean that experienced substantial changes through time in the organic carbon supply to the seafloor.

Absolute abundances of benthic foraminifers and stable isotopes from the Alvin dives 3709-3712

The presence of gas hydrates on the Blake Ridge diapir, northeastern Atlantic Ocean, offers an opportunity to study the impact of methane seepage on the ecology and geochemistry of benthic foraminifera in the late Holocene. Three push cores, covering a time span of ~ 1000 yrs, were retrieved from three distinct microhabitats at the top of the diapir at a water depth of ~ 2150 m: (i) sediments away from seepage (control core), (ii) sediments overlain by clusters of methanotrophic and thiotrophic bivalves, and (iii) chemoautotrophic microbial mats. The foraminiferal assemblages at the two seep sites are marked by a reduction in benthic foraminiferal species diversity, coupled with a near-absence of agglutinated species. However, an opportunistic population rise in CH4- or H2S-tolerant calcareous species (e.g., Globocassidulina subglobosa and Cassidulina laevigata) that utilize the abundant trophic resources at the seeps has led to an increase in the overall assemblage density there. The delta18O and delta13C values of three species of benthic foraminifera - Gyroidinoides laevigatus, Globocassidulina subglobosa, and Uvigerina peregrina - and the planktonic species Globorotalia menardii were acquired from all three cores. The benthic species from methane seeps yield delta13C values of 0.1 to - 4.2 (per mil VPDB), that are distinctly more 13C-depleted relative to the delta13C of 0.4 to - 1.0 (per mil VPDB) at the control (off seep) site. The species from a mussel-bed site exhibit more negative delta13C values than those from microbial mats, possibly reflecting different food sources and higher rate of anaerobic oxidation of methane. The positive delta13C values in the paired planktonic species suggest that authigenic carbonate precipitation did not overprint the observed 13C depletions. Hence the probable cause of negative delta13C of benthic foraminifera is primary calcification from Dissolved Inorganic Carbon (DIC) containing mixed carbon fractions from (a) highly 13C-depleted, microbially-oxidized methane and (b) a seawater source.

Stable isotopic composition of bottom water and benthic foraminifera from Hakon Mosby Mud Vulcano

To investigate the use of benthic foraminifera as a means to document ancient methane release, we determined the stable isotopic composition of tests of live (Rose Bengal stained) and dead specimens of epibenthic Fontbotia wuellerstorfi, preferentially used in paleoceanographic reconstructions, and of endobenthic high-latitude Cassidulina neoteretis and Cassidulina reniforme from a cold methane-venting seep off northern Norway. We collected foraminiferal tests from three push cores and nine multiple cores obtained with a remotely operated vehicle and a video-guided multiple corer, respectively. All sampled sites except one control site are situated at the Håkon Mosby mud volcano (HMMV) on the Barents Sea continental slope in 1250 m water depth. At the HMMV in areas densely populated by pogonophoran tube worms, d13C values of cytoplasm-containing epibenthic F. wuellerstorfi are by up to 4.4 per mil lower than at control site, thus representing the lowest values hitherto reported for this species. Live C. neoteretis and C. reniforme reach d13C values of -7.5 and -5.5 per mil Vienna Pee Dee Belemnite (VPDB), respectively, whereas d13C values of their empty tests are higher by 4 per mil and 3 per mil. However, d13C values of empty tests are never lower than those of stained specimens, although they are still lower than empty tests from the control site. This indicates that authigenic calcite precipitates at or below the sediment surface are not significantly influencing the stable isotopic composition of foraminiferal shells. The comparatively high d13C results rather from upward convection of pore water and fluid mud during active methane venting phases at these sites. These processes mingle tests just recently calcified with older ones secreted at intermittent times of less or no methane discharge. Since cytoplasm-containing specimens of suspension feeder F. wuellerstorfi are almost exclusively found attached to pogonophores, which protrude up to 3 cm above the sediment, and d13C values of bottom-water-dissolved inorganic carbon (DIC) are not significantly depleted, we conclude that low test d13C values of F. wuellerstorfi are the result of incorporation of heavily 13C-depleted methanotrophic biomass that these specimens feed on rather than because of low bottom water d13CDIC. Alternatively, the pogonophores, which are rooted at depth in the upper sediment column, may serve as a conduit for depleted d13CDIC that ultimately influences the calcification process of F. wuellerstorfi attached to the pogonophoran tube well above the sediment/water interface. The lowest d13C of live specimens of the endobenthic C. neoteretis and C. reniforme are within the range of pore water d13CDIC values, which exceed those that could be due to organic matter decomposition, and thus, in fact, document active methane release in the sediment.

Uvigerina spp. d18O and Mg/Ca measurements from sediment cores JR244-GC528 and MD07-3076

Explanations of the glacial-interglacial variations in atmospheric pCO2 invoke a significant role for the deep ocean in the storage of CO2. Deep-ocean density stratification has been proposed as a mechanism to promote the storage of CO2 in the deep ocean during glacial times. A wealth of proxy data supports the presence of a "chemical divide" between intermediate and deep water in the glacial Atlantic Ocean, which indirectly points to an increase in deep-ocean density stratification. However, direct observational evidence of changes in the primary controls of ocean density stratification, i.e., temperature and salinity, remain scarce. Here, we use Mg/Ca-derived seawater temperature and salinity estimates determined from temperature-corrected d18O measurements on the benthic foraminifer Uvigerina spp. from deep and intermediate water-depth marine sediment cores to reconstruct the changes in density of sub-Antarctic South Atlantic water masses over the last deglaciation (i.e., 22-2 ka before present). We find that a major breakdown in the physical density stratification significantly lags the breakdown of the deep-intermediate chemical divide, as indicated by the chemical tracers of benthic foraminifer d13C and foraminifer/coral 14C. Our results indicate that chemical destratification likely resulted in the first rise in atmospheric pCO2, whereas the density destratification of the deep South Atlantic lags the second rise in atmospheric pCO2 during the late deglacial period. Our findings emphasize that the physical and chemical destratification of the ocean are not as tightly coupled as generally assumed.

Benthic foraminiferal stable isotope record for the equatorial Pacific

Stable oxygen and carbon isotope (d18O and d13C) values measured in foraminiferal calcite are one of the primary tools used in paleoceanography. Diagenetic recrystallization of foraminiferal calcite can act to reset primary isotopic values, but its effects are typically poorly quantified. Here we test the impact of early stage diagenesis on stable isotope records generated from a suite of drill sites in the equatorial Pacific Ocean recovered during Ocean Drilling Program Leg 199 and Integrated Ocean Drilling Program Expedition 320. Our selected sites form paleowater and burial depth transects, with excellent stratigraphic control allowing us to confidently correlate our records. We observe large intersite differences in the preservation state of benthic foraminiferal calcite, implying very different recrystallization histories, but negligible intersite offsets in benthic d18O and d13C values. We infer that diagenetic alteration of benthic foraminiferal calcite (in sedimentary oozes) must predominantly occur at shallow burial depths (<100 m) where offsets in both the temperature and isotopic composition of waters in which the foraminifera calcified and pore waters in which diagenesis occurs are small. Our results suggest that even extensive recrystallization of benthic foraminiferal calcite results in minimal shifts from primary d18O and d13C values. This finding supports the long-held suspicion that diagenetic alteration of foraminiferal calcite is less problematic in benthic than in planktic foraminifera and that in deep-sea sediments routinely employed for paleoceanographic studies benthic foraminifera are robust recorders of stable isotope values in the fossil record.

Radon 222 excess measured on water bottle samples during HEINCKE cruise HE153

In the years 2000 and 2001 we measured methane concentrations exceeding up to two orders of magnitude the equilibrium with the atmosphere in the water column on the SW-Spitsbergen continental shelf. This methane anomaly extended from its centre on the shelf westwards over the upper slope and eastwards well into the inner basins of the two southernmost Spitsbergen fjords, the Hornsundfjord and the van Mijenfjord. Methane concentrations and stable carbon isotopic ratios varied between 2 and 240 nM, and between -53 per mill and -20 per mill VPDB, respectively. Methane in high concentrations was depleted in 13C whereas in low concentrations d13CCH4 values were highly variable. On the continental shelf we found that methane discharged from seeps on top of sandy and gravelly banks is isotopically heavier than methane escaping from troughs filled with silty and clayey sediments. These distinct isotopic signatures suggest that methane is gently released from several inter-granular seepages or micro-seepages widely spread over the shelf. A potential migration path for thermogenic or hydrate methane may be the Hornsund Fracture Zone, a south-north running reactivated fault system created by stretching of the continental crust. After discharge into the water column, local water currents fed by Atlantic water, coastal water, and freshwater outflows from the fjords further determine pathways and fate of the methane. We used d18Owater and 222Rn data to trace origin and advection of the local water masses and water mixing processes. Methane spreads predominantly along pycnoclines and by vertical mixing. During transport methane is influenced simultaneously by oxidation and dilution, as well as loss into the atmosphere. Together these processes cause the spatial variability of the anomaly and heterogeneity in d13CCH4 in this polar shelf environment.

Stable isotope ratios, carbon content and primary production of three sediment cores from the subantarctic eastern Atlantic

We present three new benthic foraminiferal delta13C, delta18O, and total organic carbon time series from the eastern Atlantic sector of the Southern Ocean between 41°S and 47°S. The measured glacial delta13C values belong to the lowest hitherto reported. We demonstrate a coincidence between depleted late Holocene (LH) delta13C values and positions of sites relative to ocean surface productivity. A correction of +0.3 to +0.4 [per mil VPDB] for a productivity-induced depletion of Last Glacial Maximum (LGM) benthic delta13C values of these cores is suggested. The new data are compiled with published data from 13 sediment cores from the eastern Atlantic Ocean between 19°S and 47°S, and the regional deep and bottom water circulation is reconstructed for LH (4-0 ka) and LGM (22-16 ka) times. This extends earlier eastern Atlantic-wide synoptic reconstructions which suffered from the lack of data south of 20°S. A conceptual model of LGM deep-water circulation is discussed that, after correction of southernmost cores below the Antarctic Circumpolar Current (ACC) for a productivity-induced artifact, suggests a reduced formation of both North Atlantic Deep Water in the northern Atlantic and bottom water in the southwestern Weddell Sea. This reduction was compensated for by the formation of deep water in the zone of extended winter sea-ice coverage at the northern rim of the Weddell Sea, where air-sea gas exchange was reduced. This shift from LGM deep-water formation in the region south of the ACC to Holocene bottom water formation in the southwestern Weddell Sea, can explain lower preformed d13CDIC values of glacial circumantarctic deep water of approximately 0.3 per mil to 0.4 per mil. Our reconstruction brings Atlantic and Southern Ocean d13C and Cd/Ca data into better agreement, but is in conflict, however, with a scenario of an essentially unchanged thermohaline deep circulation on a global scale. Benthic delta18O-derived LGM bottom water temperatures, by 1.9°C and 0.3°C lower than during the LH at deepest southern and shallowest northern sites, respectively, agree with the here proposed reconstruction of deep-water circulation in the eastern South Atlantic Ocean.