Long chain diols and diol indices of surface sediments of the Iberian Atlantic margin

Long chain diols are lipids that have gained interest over the last years due to their high potential to serve as biomarkers and diol indices have been proposed to reconstruct upwelling conditions and sea surface temperature (SST). However, little is known about the sources of the diols and the mechanisms impacting their distribution. Here we studied the factors controlling diol distributions in the Iberian Atlantic margin, which is characterized by a dynamic continental shelf under the influence of upwelling of nutrient-rich cold deep waters, and fluvial input. We analyzed suspended particulate matter (SPM) of the Tagus river, marine SPM and marine surface sediments along five transects off the Iberian margin, as well as riverbank sediments and soil from the catchment area of the Tagus river. Relatively high fractional abundances of the C32 1,15-diol (normalized with respect to the 1,13- and 1,15-diols) were observed in surface sediments in front of major river mouths and this abundance correlates strongly with the BIT index, a tracer for continental input of organic carbon. Together with an even higher fractional abundance of the C32 1,15-diol in the Tagus river SPM, and the absence of long chain diols in the watershed riverbank sediments and soils, we suggest that this long chain diol is produced in-situ in the river. Further support for this hypothesis comes from the small but distinct stable carbon isotopic difference of 1.3? with the marine C28 1,13-diol. The 1,14-diols are relatively abundant in surface sediments directly along the northern part of the coast, close to the upwelling zone, suggesting that Diol Indices based on 1,14-diols would work well as upwelling tracers in this region. Strikingly, we observed a significant difference in stable carbon isotopic composition between the monounsaturated C30:1 1,14- and the saturated C28 1,14-diol (3.8±0.7 per mil), suggesting different sources, in accordance with their different distributions. In addition, the Long chain Diol Index (LDI), a proxy for sea surface temperature, was applied for the surface sediments. The results correlate well with satellite SSTs offshore but reveal a significant discrepancy with satellite-derived SSTs in front of the Tagus and Sado rivers. This suggests that river outflow might compromise the applicability of this proxy.

Isotope analysis and heat flow measurements of Maria S. Merian cruise MSM21/4 on the western Svalbard margin

Methane hydrate is an ice-like substance that is stable at high-pressure and low temperature in continental margin sediments. Since the discovery of a large number of gas flares at the landward termination of the gas hydrate stability zone off Svalbard, there has been concern that warming bottom waters have started to dissociate large amounts of gas hydrate and that the resulting methane release may possibly accelerate global warming. Here, we can corroborate that hydrates play a role in the observed seepage of gas, but we present evidence that seepage off Svalbard has been ongoing for at least three thousand years and that seasonal fluctuations of 1-2°C in the bottom-water temperature cause periodic gas hydrate formation and dissociation, which focus seepage at the observed sites.

(Table 2) Age determination of sediment cores from the Portuguese Margin

We demonstrate that changes in the behavior of the Mediterranean Outflow Water (MOW) prior to and through the last deglaciation played an important role in promoting Meridional Overturning Circulation (MOC). Estimation of past MOW salt and heat fluxes indicates that they gradually increased through the last deglaciation. Between 17.5 and 14.6 thousand years ago (ka B.P., where B.P. references year 1950), net evaporation from the Mediterranean exported sufficient fresh water from the North Atlantic catchment to cause an average salinity increase of 0.5 psu throughout the upper 2000 m of the entire North Atlantic to the north of 25°N. Combined with rapid intensification and shoaling of the MOW plume, which we identify around 15-14.5 ka B.P., this deglacial MOW-related salt accumulation preconditioned the North Atlantic for abrupt resumption of the MOC at 14.6 ka B.P.

Distribution of surface sediment properties along the Portuguese western margin

Organic matter contained in surface sediments from four regions on the western Portuguese shelf, which are influenced by coastal upwelling and fluvial input, was analysed with respect to elemental organic carbon (Corg) and nitrogen (Ntotal) content and isotopic carbon and nitrogen ratios (d13Corg, d15N). Corg/Ntotal weight ratios and d13Corg values are interpreted in terms of terrigenous or marine organic matter sources, supported by CaCO3 content. Organic matter in the shelf sediments is mainly of marine origin, with increasing terrigenous components only close to rivers and estuaries. In the northern shelf region the data indicates significant terrigenous supply by the Douro River. North of the Nazaré Canyon organic matter composition implies a mainly marine origin, with a higher terrestrial influence close to the canyon head. Organic matter composition in the central shelf region, which is dominated by the Tagus Estuary and the Tagus prodelta, reveals a change from a continental-type signature within the estuary to a more marine-type signature further to the west and south of the estuary mouth. In the southern region near Cape Sines the geochemical properties clearly reflect the marine origin of sedimentary organic matter. Sedimentary d15N values are interpreted to reflect various degrees of assimilation of seasonally upwelled nitrate, in relation to the upwelling centres. In the estuarine environment, inputs of agriculturally influenced dissolved inorganic nitrogen are reflected in the sediments. No evidence for N2-fixation or denitrification is found. On the central shelf north of the Nazaré canyon, sedimentary d15N values are close to marine d15NO3- and thus indicate a complete NO3- assimilation and N-limitation of marine production. Light d15N values in distal sediments off the Douro River mouth and in samples south of C. Sines reflect high NO3- supply and a close proximity to the seasonal upwelling centres. Particularly in sediments form the Sines region, light d15N values in southern samples reflect stronger upwelling further south.

Sea surface temperature and export productivity reconstructions of sediments off the western Iberian margin

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.

(Figure 4) Stable carbon isotopic values and relative contents of biphytanes and sugars from sediment sample from the Peru margin and from the Pakistan margin

Glycolipids are prominent constituents in the membranes of cells from all domains of life. For example, diglycosyl-glycerol dibiphytanyl glycerol tetraethers (2Gly-GDGTs) are associated with methanotrophic ANME-1 archaea and heterotrophic benthic archaea, two archaeal groups of global biogeochemical importance. The hydrophobic biphytane moieties of 2Gly-GDGTs from these two uncultivated archaeal groups exhibit distinct carbon isotopic compositions. To explore whether the isotopic compositions of the sugar headgroups provide additional information on the metabolism of their producers, we developed a procedure to analyze the d13C values of glycosidic headgroups. Successful determination was achieved by (1) monitoring the contamination from free sugars during lipid extraction and preparation, (2) optimizing the hydrolytic conditions for glycolipids, and (3) derivatizing the resulting sugars into aldononitrile acetate derivatives, which are stable enough to withstand a subsequent column purification step. First results of d13C values of sugars cleaved from 2Gly-GDGTs in two marine sediment samples, one containing predominantly ANME-1 archaea and the other benthic archaea, were obtained and compared with the d13C values of the corresponding biphytanes. In both samples the dominant sugar headgroups were enriched in 13C relative to the corresponding major biphytane. This 13C enrichment was significantly larger in the putative major glycolipids from ANME-1 archaea (~15 per mil) than in those from benthic archaea (<7 per mil). This method opens a new analytical window for the examination of carbon isotopic relationships between sugars and lipids in uncultivated organisms.

(Table 2) Carbonate chemistry and isotopes from northern Cascadia margin samples

Most authigenic carbonates previously recovered from the Cascadia slope have 87Sr/86Sr signatures that reflect shallow precipitation in equilibrium with coeval seawater. There is also evidence for carbonate formation supported by fluids that have been modified by reactions with the incoming Juan de Fuca plate (87Sr/86Sr = 0.7071; Teichert et al., 2005, doi:10.1016/j.epsl.2005.08.002) or with terrigenous turbidites (87Sr/86Sr = 0.70975 to 0.71279; Sample et al., 1993, doi:10.1130/0091-7613(1993)021<0507:CCICFF>2.3.CO;2). We report on the strontium isotopic composition of carbonates and fluids from IODP Site U1329 and nearby Barkley Canyon (offshore Vancouver Island), which have strontium isotope ratios as low as 0.70539. Whereas the strontium and oxygen isotopic compositions of carbonates from paleoseeps in the uplifted Coast Range forearc indicate formation in ambient bottom seawater, several samples from the Pysht/Sooke Fm. show a 87Sr-depleted signal (87Sr/86Sr = 0.70494 and 0.70511) similar to that of the anomalous Site U1329 and Barkley Canyon carbonates. Our data, when analyzed in the context of published elemental and isotopic composition of these carbonates (Joseph et al., 2012, doi:10.1016/j.palaeo.2013.01.012 ), point to two formation mechanisms: 1) shallow precipitation driven by the anaerobic oxidation of methane (AOM) with d13C values as low as -50 per mil and contemporaneous 87Sr/86Sr seawater ratios, and 2) carbonate precipitation driven by fluids that have circulated through the oceanic crust, which are depleted in 87Sr. Carbonates formed from the second mechanism precipitate both at depth and at sites of deep-sourced fluid seepage on the seafloor. The 87Sr-depleted carbonates and pore fluids found at Barkley Canyon represent migration of a deep, exotic fluid similar to that found in high permeability conglomerate layers at 188 mbsf of Site U1329, and which may have fed paleoseeps in the Pysht/Sooke Fm. These exotic fluids likely reflect interaction with the 52-57 Ma igneous Crescent Terrane, which supplies fluids with high calcium, manganese and strontium enriched in the non-radiogenic nucleide. Tectonic compression and dehydration reactions then force these fluids updip, where they pick up the thermogenic hydrocarbons and 13C-enriched dissolved inorganic carbon that are manifested in fluids and carbonates sampled at Barkley Canyon and at Site U1329. The Crescent Terrane may have sourced cold seeps in this margin since at least the late Oligocene.

Pigments of sediment cores of the Northwest European Continental Margin

In the context of the European OMEX Programme this investigation focused on gradients in the biomass and activity of the small benthic size spectrum along a transect across the Goban Spur from the outer Celtic Sea into Porcupine Abyssal Plain. The effects of food pulses (seasonal, episodic) on this part of the benthic size spectrum were investigated. Sediments sampled during eight expeditions at different seasons covering a range from 200 m to 4800 m water depth were assayed with biochemical bulk measurements: determinations of chloroplastic pigment equivalents (CPE), the sum of chlorophyll a and its breakdown products, provide information concerning the input of phytodetrital matter to the seafloor; phospholipids were analyzed to estimate the total biomass of small benthic organisms (including bacteria, fungi, flagellata, protozoa and small metazoan meiofauna). A new term 'small size class biomass' (SSCB) is introduced for the biomass of the smallest size classes of sediment-inhabiting organisms; the reduction of fluorescein-di-acetate (FDA) was determined to evaluate the potential activity of ester-cleaving bacterial exoenzymes in the sediment samples. At all stations benthic biomass was predominantly composed of the small size spectrum (90% on the shelf; 97-98% in the bathyal and abyssal parts of the transect). Small size class biomass (integrated over a 10 cm sediment column) ranged from 8 g C/m**2 on the shelf to 2.1 g C/m**2 on the adjacent Porcupine Abyssal Plain, exponentially decreasing with increasing water depth. However, a correlation between water depth and SSCB, macrofauna biomass as well as metazoan meiofauna biomass exhibited a significantly flatter slope for the small size classes in comparison to the larger organisms. CPE values indicated a pronounced seasonal cycle on the shelf and upper slope with twin peaks of phytodetrital deposition in mid spring and late summer. The deeper stations seem to receive a single annual flux maximum in late summer. SSCB and heterotrophic activity are significantly correlated to the amount of sediment-bound pigments. Seasonality in pigment concentrations is clearly followed by SSCB and activity. In contrast to macro- and megafauna which integrate over larger periods (months/years), the small benthic size classes, namely bacteria and foraminifera, proved to be the most reactive potential of the benthic communities to any perturbations on short time scales (days/weeks). The small size classes, therefore, occupy a key role in early diagenetic processes.