(Table 1) Mean grain sizes and standard deviations of gas hydrate samples

Methane hydrates are present in marine seep systems and occur within the gas hydrate stability zone. Very little is known about their crystallite sizes and size distributions because they are notoriously difficult to measure. Crystal size distributions are usually considered as one of the key petrophysical parameters because they influence mechanical properties and possible compositional changes, which may occur with changing environmental conditions. Variations in grain size are relevant for gas substitution in natural hydrates by replacing CH4 with CO2 for the purpose of carbon dioxide sequestration. Here we show that crystallite sizes of gas hydrates from some locations in the Indian Ocean, Gulf of Mexico and Black Sea are in the range of 200-400 µm; larger values were obtained for deeper-buried samples from ODP Leg 204. The crystallite sizes show generally a log-normal distribution and appear to vary sometimes rapidly with location.

Gut content of holothurians from the NE Atlantic

This paper describes inter-specific differences in the distribution of sediment in the gut compartments and in the enzyme and bacterial profiles along the gut of abyssal holothurian species - Oneirophanta mutabilis, Psychropotes longicauda and Pseudostichopus villosus sampled from a eutrophic site in the NE Atlantic at different times of the year. Proportions of sediments, relative to total gut contents, in the pharynx, oesophagus, anterior and posterior intestine differed significantly in all the inter-species comparisons, but not between inter-seasonal comparisons. Significant differences were also found between the relative proportions of sediments in both the rectum and cloaca of Psychropotes longicauda and Oneirophanta mutabilis. Nineteen enzymes were identified in either gut-tissue or gut-content samples of the holothurians studied. Concentrations of the enzymes in gut tissues and their contents were highly correlated. Greater concentrations of the enzymes were found in the gut tissues suggesting that they are the main source of the enzymes. The suites of enzymes recorded were broadly similar in each of the species sampled collected regardless of the time of the year, and they were similar to those described previously for shallow-water holothurians. Significant inter-specific differences in the gut tissue concentrations of some of the glycosidases suggest dietary differences. For example, Psychropotes longicauda and Pseudostichopus villosus contain higher levels of chitobiase than Oneirophanta mutabilis. There were no seasonal changes in bacterial activity profiles along the guts of O. mutabilis and Pseudostichopus villosus. In both these species bacterial activity and abundance declined between the pharynx/oesophagus and anterior intestine, but then increased along the gut and became greatest in the rectum/cloaca. Although the data sets were more limited for Psychropotes longicauda, bacterial activity increased from the anterior to the posterior intestine but then declined slightly to the rectum/cloaca. These changes in bacterial activity and densities probably reflect changes in the microbial environment along the guts of abyssal holothurians. Such changes suggest that there is potential for microbial breakdown of a broader range of substrates than could be otherwise be achieved by the holothurian itself. However, the present study found no evidence for sedimentary (microbial) sources of hydrolytic enzymes.

Age model, radiocarbon dates and dinoflagellate cyst measurements from sediment core DA06-139G

A marine sediment core from Vaigat in Disko Bugt, West Greenland, has been analysed in terms of lithology, dinoflagellate cysts and foraminifera in order to evaluate the influence of oceanographic variability on West Greenland glacier stability. The data show that during the past 5200 years the Atlantic foraminiferal abundance in the subsurface waters of the West Greenland Current (WGC) episodically increased, indicating periods of increases in the inflow of subsurface warm Atlantic water at 2000 - 1500 cal. yr BP and 1300 cal. yr BP as well as periods of less pronounced increased bottom-water temperatures around 4700 - 4000 cal. yr BP, 3100 - 2800, 2600, 1000 - 800, 500 - 400, and at 200 cal. yr. The sedimentological and dinoflagellate cyst data indicate that these episodes with enhanced advection of Irminger Sea-derived waters are accompanied by increased iceberg rafting, which we link to increased iceberg calving in relation to destabilization of the Jakobshavn Isbrae. The long-term trend in the data documents the end of a late-Holocene Thermal Maximum between 5200 and 4300 cal. yr BP and a final onset of the Neoglaciation at 3500 cal. yr BP. Increased responses of the iceberg rafting after 3500 cal. yr BP, reflects a westward/seaward advance of the glacier margin in relation to onset of Neoglaciation and a development of the glacier into a floating tongue after 2000 cal. yr BP. A comparison of our record with a record from the eastern North Atlantic indicates that a NAO-like anomaly pattern between subsurface waters in West Greenland and atmospheric temperature in the Eastern North Atlantic may have been operating during most of the late Holocene. However, during the past 1000 years the NAO signal may have weakened as some other mode of climate variability overprints the anti-phase climate signal in this region.

Sedimentology and paleontology on core Lz1104 from Lake Hjort, Greenland

Two sediment cores of 70 and 252 cm length were recovered from Hjort Sø, a small lake on Store Koldewey, Northeast Greenland, and studied with a multidisciplinary approach in order to reconstruct the local environmental history and to test the relevance of proxies for paleoenvironmental information. The basal sediments from the longer core are dominated by clastic matter, which was likely deposited during deglaciation of the lake basin. These clastic sediments are overlain by gyttja, which is also present throughout the shorter core. AMS radiocarbon dating was conducted on plant macrofossils of 11 samples from the gyttja in both cores. A reliable chronology was established for both cores, which dated the onset of organic accumulation at 9,500 cal. year BP. The Holocene temperature development, with an early to mid Holocene thermal maximum, is best reflected in the grain-size composition. Nutrient availability was apparently low during the early Holocene and led to low productivity in the lake and its vicinity. From ca. 7,000 cal. year BP, productivity in the lake increased significantly, probably induced by external nutrient input from goose excrements. From this time, micro- and macrofossil remains reflect relatively well the climate history of East Greenland, with a cooling during the middle Holocene, the medieval warming, and the Little Ice Age. The amount of organic matter in the sequence seems to be more affected by lake ice cover or by nutrient supply from the catchment than by temperature changes. The record from Hjort Sø thus reveals the difficulties in interpreting sedimentary records from high arctic regions.

Calcareous nannofossils in Neogene sediments of ODP Leg 117 holes

Calcareous nannofossils were studied in 574 Neogene samples recovered from eight sites drilled in block-faulted basins on the continental margin of Oman. This portion of the Arabian Sea experiences seasonal upwelling associated with the southwest monsoon. Not surprisingly, some of the more typical Neogene warm-water nannoplankton are either missing entirely or are extremely rare in these sediments. Coccolithus pelagicus, a typical cold-water indicator, is extremely abundant in many samples of late Pliocene to early Pleistocene age. These intervals correspond to periods of Northern Hemisphere glaciation. Reworked Late Cretaceous and Cenozoic nannofossils are found in a majority of the samples. They were probably carried from the Arabian Peninsula or the continent of Africa on strong southwest summer winds. Ages for the various nannofossil events were calculated by projecting the nannofossil datums onto the magnetostratigraphic scale for Sites 724, 727, and 728. These are the first ages for the various nannofossil datums derived from Oman Margin sediments. The following ages have been calculated for these nannofossil events: FAD Emiliania huxleyi, 0.23 Ma; LAD Pseudoemiliania lacunosa, 0.38 Ma; FAD Helicosphaera inversa, 0.42 Ma; top of acme of Reticulofenestra sp. A, 0.70 Ma; FAD Gephyrocapsaparallela, 0.85 Ma; LAD Gephyrocapsa spp. (large), 1.07 Ma; LAD Helicosphaera sellii, 1.34 Ma; LAD Calcidiscus macintyrei, 1.47 Ma; FAD Gephyrocapsa oceanica, 1.53 Ma; FAD Gephyrocapsa caribbeanica, 1.80 Ma; LAD Discoaster brouweri, 2.03 Ma; LAD Discoasterpentaradiatus, 2.31 Ma; LAD Discoaster surculus, 2.42; LAD Discoaster tamalis, 2.77 Ma; LAD Sphenolithus abies, 3.44 Ma; and LAD Reticulofenestra pseudoumbilica, 3.44 Ma.

Sea-surface temperature reconstructions for the Quaternary western Atlantic

Paleotemperature estimates calculated by the SIMMAX Modern Analog Technique are presented for two gravity cores from the Rio Grande Rise, one from the Brazil Slope, and one from the Ceara Rise. The estimates are based on comparisons between modern and fossil planktonic foraminiferal assemblages and were carried out on samples from Quaternary sediments. Estimated warm-season temperatures from the Rio Grande Rise (at approx. 30° S) range from around 19°C to 24°C, with some coincidence of warm peaks with interglacial stages. The temperature estimates (also warm-season) from the more tropical Brazil Slope (at approx. 8° S) and Ceara Rise (at approx. 4° N) cores are more stable, remaining between 26°C and 28°C throughout most of their lengths. This fairly stable situation in the tropical western Atlantic is interrupted in oxygen isotope stage 6 by a significant drop of 2-3°C in both of these cores. Temperature estimates from the uppermost samples in all cores compare very well to the modern-day measured values. Affinities of some foraminiferal species for warmer or cooler surface temperatures are identified within the temperature range of the examined samples based on their abundance values. Especially notable among the warmer species are, Globorotalia menardii, Globigerinita glutinata, Globigerinoides ruber, and Globigerinoides sacculifer. Species indicative of cooler surface temperatures include Globorotalia inflata, Globigerina bulloides, Neogloboquadrina pachyderma, and Globigerina falconensis. A cluster analysis was carried out to assist in understanding the degree of variation which occurs in the foraminiferal assemblages, and how temperature differences influence the faunal compositions of the samples. It is demonstrated that fairly similar samples may have unexpectedly different estimated temperatures due to small differences in key species and, conversely, quite different assemblages can result in similar or identical temperature estimates which confirms that other parameters than just temperature affect faunal content.

(Table 1) Age determination of Arctic Ocean sediment cores

Accelerator mass spectrometer 14C dated stable isotope data from Neogloboquadrina pachyerma in cores raised from the Mendeleyev Ridge and slope provide evidence for significant influx of meltwater to the western Arctic Ocean during the early part of marine oxygen isotope stage 1 (OIS 1) and during several intervals within OIS 3. The strongest OIS 3 meltwater event occurred before ca. 45 ka (conventional radiocarbon age) and was probably related to the deglaciation at the beginning of OIS 3. Major meltwater input to the western Arctic Ocean during the last deglaciation coincides closely with the maximum rate of global sea-level rise as determined from the Barbados sea-level record, demonstrating a strong link between the global record and changes in the central Arctic Ocean. OIS 2, which includes the last glacial maximum, is very condensed or absent in the cores. Abundance and d13C values for N. pachyderma in the middle part of OIS 3 are similar to modern values, indicating high productivity and seasonal ice-free areas along the Arctic margin at that time. These records indicate that the Arctic Ocean was a source of heat and moisture to the northern polar atmosphere during parts of OIS 3.

Geochemistry of microtektites from Victoria Land Transantarctic Mountains

We extended the petrographic and geochemical dataset for the recently discovered Transantarctic Mountain microtektites in order to check our previous claim that they are related to the Australasian strewn field. Based on color and composition, the 465 microtektites so far identified include two groups of transparent glass spheres less than ca. 800 µm in diameter: the most abundant pale-yellow, or normal, microtektites, and the rare pale-green, or high-Mg, microtektites. The major element composition of normal microtektites determined through electron microprobe analysis is characterized by high contents of silica (SiO2 = 71.5 ± 3.6 (1 sigma) wt%) and alumina (Al2O3 = 15.5 ± 2.2 (1 sigma) wt%), low total alkali element contents (0.50-1.85 wt%), and MgO abundances <6 wt%. The high-Mg microtektites have a distinctly higher MgO content >10 wt%. Transantarctic Mountain microtektites contain rare silica-rich (up to 93 wt% SiO2) glassy inclusions similar to those found in two Australasian microtektites analyzed here for comparison. These inclusions are interpreted as partially digested, lechatelierite-like inclusions typically found in tektites and microtektites. The major and trace element (by laser ablation - inductively coupled plasma - mass spectrometry) abundance pattern of the Transantarctic Mountain microtektites matches the average upper continental crust composition for most elements. Major deviations include a strong to moderate depletion in volatile elements including Pb, Zn, Na, K, Rb, Sr and Cs, as a likely result of severe volatile loss during the high temperature melting and vaporization of crustal target rocks. The normal and high-Mg Transantarctic Mountain microtektites have compositions similar to the most volatile-poor normal and high-Mg Australasian microtektites reported in the literature. Their very low H2O and B contents (by secondary ion mass spectrometry) of 85 ± 58 (1 sigma) ?g/g and 0.53 ± 0.21 ?g/g, respectively, evidence the extreme volatile loss characteristically observed in tektites. The Sr and Nd isotopic compositions of multigrain samples of Transantarctic Mountain microtektites are 87Sr/86Sr ~ 0.71629 and 143Nd/144Nd ~ 0.51209, and fall into the Australasian tektite compositional field. The Nd model age calculated with respect to the chondritic uniform reservoir (CHUR) is TNdCHUR ~ 1.1 Ga, indicating a Meso-Proterozoic crustal source rock, as was derived for Australasian tektites as well. Coupled with the Quaternary age from the literature, the extended dataset presented in this work strengthens our previous conclusion that Transantarctic Mountain microtektites represent a major southward extension of the Australasian tektite/microtektite strewn field. Furthermore, the significant depletion in volatile elements (i.e., Pb, B, Na, K, Zn, Rb, Sr and Cs) of both normal and high-Mg Transantarctic Mountain microtektites relative to the Australasian ones provide us with further confirmation of a possible relationship between high temperature-time regimes in the microtektite-forming process and ejection distance.

Temperature, salinity, methane concentration, oxidation rates and methanotrophic cell number at Svalbard seeps in summer 2011 and 2012 (cruises POS419 and MSM21/4)

Large amounts of the greenhouse gas methane are released from the seabed to the water column where it may be consumed by aerobic methanotrophic bacteria. This microbial filter is consequently the last marine sink for methane before its liberation to the atmosphere. The size and activity of methanotrophic communities, which determine the capacity of the water column methane filter, are thought to be mainly controlled by nutrient and redox dynamics, but little is known about the effects of ocean currents. Here, we report measurements of methanotrophic activity and biomass (CARD-FISH) at methane seeps west of Svalbard, and related them to physical water mass properties (CTD) and modelled current dynamics. We show that cold bottom water containing a large number of aerobic methanotrophs was rapidly displaced by warmer water with a considerably smaller methanotrophic community. This water mass exchange, caused by short-term variations of the West Spitsbergen Current, constitutes a rapid oceanographic switch severely reducing methanotrophic activity in the water column. Strong and fluctuating currents are widespread oceanographic features common at many methane seep systems and are thus likely to globally affect methane oxidation in the ocean water column.

Age determinations and stable isotope records of four sediment profiles off Nova Scotia

Continental margin sediments off Nova Scotia accumulate at high rates (up to 360 cm/kyr) and contain a history of millennial-scale environmental changes which are dominated by the proximity of the Laurentide ice sheet during the latest Quaternary. Using stable isotope ratios of oxygen, accelerator mass spectrometer radiocarbon dating, micropaleontology, and sedimentology, we document these changes in six piston cores ranging in water depth from ab. 450 to ab. 4300 m. We find that maximum d18O in N. pachyderma occurred about 15 ka and preceded the maximum abundance of this species in these cores by ab. 1000 years. Between 13 and 14 ka we find a second peak in abundance of N. pachyderma, minimum d18O, and two pulses of ice rafting. The sediment lithology supports terrestrial studies which indicate that there was a general withdrawal of ice beyond the upper Paleozoic and Mesozoic red beds by 14 ka in southeastern Canada, so the ice rafting events between 13 and 14 ka probably reflect ice stream activity in the St. Lawrence valley. The Younger Dryas event is recognized as a peak in abundance of N. pachyderma and ice rafting (dated as ab. 11.3 ka), but meltwater discharge to the Gulf of St. Lawrence was either too small or occurred over too long a time to leave a distinct d18O minimum off Nova Scotia. At 7.1 ka, in the middle of Holocene warming, we find a third peak in abundance of N. pachyderma and another d18O minimum but no ice rafting. We interpret these data as evidence of a late-occurring meltwater event which, if correct, could have originated in the Great Lakes, in the Labrador-Ungava region, or in both. The final millennial-scale phenomenon off Nova Scotia is the onset of "Neoglaciation," marked by increased ice rafting and increased % N. pachyderma beginning about 5 kyr ago.

14C concentrations of algal and archaeal lipids and their associated sea surface temperature proxies in the Black Sea

Understanding the preservation and deposition history of organic molecules is crucial for the understanding of paleoenvironmental information contained in their abundance ratios such as Uk'37 and TEX86 used as proxies for sea surface temperature (SST). Based on their relatively high refractivity, alkenones and glycerol dialkyl glycerol tetraethers (GDGTs) can survive postdepositional processes like lateral transport, potentially causing inferred SSTs to be misleading. Likewise, selective preservation of alkenones and GDGTs may cause biases of the SST proxies themselves and can lead to decoupling of both proxy records. Here we report compound-specific radiocarbon data of marine biomarkers including alkenones, GDGTs, and low molecular weight (LMW) n-fatty acids from Black Sea sediments deposited under different redox regimes to evaluate the potentially differential preservation of both biomarker classes and its effect on the SST indices Uk'37 and TEX86 . The decadal D14C values of alkenones, GDGTs, and LMW n-fatty acids indicate similar preservation under oxic, suboxic, and anoxic redox regimes and no contribution of pre-aged compounds, e.g., by lateral supply. Moreover, similar 14C concentrations of crenarchaeol, alkenones, and LMW n-fatty acids imply that the thaumarchaeotal GDGTs preserved in these sediments are produced in the euphotic zone rather than in subsurface/thermocline waters. However, we observe biomarker-based SSTs that strongly deviate (deltaSST up to 8.4 °C) from in situ measured mean annual SSTs in the Black Sea. This is not due to redox-dependent differential biomarker preservation as implied by their D14C values and spatial SST pattern. Since contributions from different sources can largely be excluded, the deviation of the Uk'37 and TEX86 proxy-derived SSTs from in situ SSTs requires further study of phylogenetic and other yet unknown environmental controls on alkenone and GDGT lipid distributions in the Black Sea.

Response of spring diatoms to CO2 availability in the Western North Pacific as determined by next-generation sequencing

Next-generation sequencing (NGS) technologies have enabled us to determine phytoplankton community compositions at high resolution. However, few studies have adopted this approach to assess the responses of natural phytoplankton communities to environmental change. Here, we report the impact of different CO2 levels on spring diatoms in the Oyashio region of the western North Pacific as estimated by NGS of the diatom-specific rbcL gene (DNA), which encodes the large subunit of RubisCO. We also examined the abundance and composition of rbcL transcripts (cDNA) in diatoms to assess their physiological responses to changing CO2 levels. A short-term (3-day) incubation experiment was carried out on-deck using surface Oyashio waters under different pCO2 levels (180, 350, 750, and 1000 µatm) in May 2011. During the incubation, the transcript abundance of the diatom-specific rbcL gene decreased with an increase in seawater pCO2 levels. These results suggest that CO2 fixation capacity of diatoms decreased rapidly under elevated CO2 levels. In the high CO2 treatments (750 and 1000 µatm), diversity of diatom-specific rbcL gene and its transcripts decreased relative to the control treatment (350µatm), as well as contributions of Chaetocerataceae, Thalassiosiraceae, and Fragilariaceae to the total population, but the contributions of Bacillariaceae increased. In the low CO2 treatment, contributions of Bacillariaceae also increased together with other eukaryotes. These suggest that changes in CO2 levels can alter the community composition of spring diatoms in the Oyashio region. Overall, the NGS technology provided us a deeper understanding of the response of diatoms to changes in CO2 levels in terms of their community composition, diversity, and photosynthetic physiology.

Antarctic crustacean grazer assemblages exhibit resistance following exposure to decreased pH

Anthropogenic atmospheric CO2 concentrations are increasing rapidly, resulting in declining seawater pH (ocean acidification). The majority of ocean acidification research to date has focused on the effects of decreased pH in single-species experiments. To assess how decreased pH may influence natural macroalgal-grazer assemblages, we conducted a mesocosm experiment with the common, chemically defended Antarctic brown macroalga Desmarestia menziesii and natural densities of its associated grazer assemblage, predominantly amphipods. Grazer assemblages were collected from the immediate vicinity of Palmer Station (64°46'S, 64°03'W) in March 2013. Assemblages were exposed for 30 days to three levels of pH representing present-day mean summer ambient conditions (pH 8.0), predicted near-future conditions (2100, pH 7.7), and distant-future conditions (pH 7.3). A significant difference was observed in the composition of mesograzer assemblages in the lowest pH treatment (pH 7.3). The differences between assemblages exposed to pH 7.3 and those maintained in the other two treatments were driven primarily by decreases in the abundance of the amphipod Metaleptamphopus pectinatus with decreasing pH, reduced copepod abundance at pH 7.7, and elevated ostracod abundance at pH 7.7. Generally, the assemblages maintained at pH 7.7 were not significantly different from those at ambient pH, demonstrating resistance to short-term decreased pH. The relatively high prevalence of generalist amphipods may have contributed to a net stabilizing effect on the assemblages exposed to decreased pH. Overall, our results suggest that crustacean grazer assemblages associated with D. menziesii, the dominant brown macroalgal species of the western Antarctic Peninsula, may be resistant to short-term near-future decreases in seawater pH.

Neodymium isotopic characterization of Ross Sea Bottom Water and its advection through the southern South Pacific, POLARSTERN cruise ANT-XXVI/2

Since the inception of the international GEOTRACES program, studies investigating the distribution of trace elements and their isotopes in the global ocean have significantly increased. In spite of this large-scale effort, the distribution of neodymium isotopes (143Nd/144Nd) and concentrations ([Nd]) in the high latitude south Pacific is still understudied. Here we report dissolved Nd isotopes and concentrations from 11 vertical water column profiles from the south Pacific between South America and New Zealand. Results suggest that Ross Sea Bottom Water (RSBW) is represented by an epsilon-Nd value of ~ -7, and is thus more radiogenic than Circumpolar Deep Water (epsilon-Nd ~ -8). RSBW and its characteristic epsilon-Nd signature can be traced far into the SE Pacific until progressive mixing with ambient Lower Circumpolar Deep water (LCDW) dilutes this signal north of the Antarctic Polar Front (APF). The SW-NE trending Pacific-Antarctic Ridge restricts the advection of RSBW into the SW Pacific, where bottom water density, salinity, and epsilon-Nd values of -9 indicate the presence of bottom waters of an origin different from the Ross Sea. Neodymium concentrations show low surface concentrations and a linear increase with depth north of the Polar Front. South of the APF, surface [Nd] is high and increases with depth but remains almost constant below ~1000 m. This vertical and spatial [Nd] pattern follows the southward shoaling density surfaces of the Southern Ocean frontal system and hence suggests supply of Nd to the upper ocean through upwelling of Nd-rich deep water. Low particle abundance dominated by reduced opal production and seasonal sea ice cover likely contributes to the maintenance of the high upper ocean [Nd] south of the APF. The reported data highlights the use of Nd isotopes as a water mass tracer in the Southern Ocean, with the potential for paleocenaographic reconstructions, and contributes to an improved understanding of Nd biogeochemistry.

Carbonates and selected geochemistry composition for sediments from Lake Iznik for the past 31 ka cal BP

This study examines the forcing mechanisms driving long-term carbonate accumulation and preservation in lacustrine sediments in Lake Iznik (northwestern Turkey) since the last glacial. Currently, carbonates precipitate during summer from the alkaline water column, and the sediments preserve aragonite and calcite. Based on X-ray diffraction data, carbonate accumulation has changed significantly and striking reversals in the abundance of the two carbonate polymorphs have occurred on a decadal time scale, during the last 31 ka cal BP. Different lines of evidence, such as grain size, organic matter and redox sensitive elements, indicate that reversals in carbonate polymorph abundance arise due to physical changes in the lacustrine setting, for example, water column depth and lake mixing. The aragonite concentrations are remarkably sensitive to climate, and exhibit millennial-scale oscillations. Extending observations from modern lakes, the Iznik record shows that the aerobic decomposition of organic matter and sulphate reduction are also substantial factors in carbonate preservation over long time periods. Lower lake levels favour aragonite precipitation from supersaturated waters. Prolonged periods of stratification and consequently enhanced sulphate reduction favour aragonite preservation. In contrast, prolonged or repeated exposure of the sediment-water interface to oxygen results in in situ aerobic organic matter decomposition, eventually leading to carbonate dissolution. Notably, the Iznik sediment profile raises the hypothesis that different states of lacustrine mixing lead to selective preservation of different carbonate polymorphs. Thus, a change in the entire lake water chemistry is not strictly necessary to favour the preservation of one polymorph over another.