Biomarkers in surface sediments from the Ob and Yenisei estuaries and the southern Kara Sea

Organic-geochemical bulk parameter (Total organic carbon contents, C/N ratios and d13Corg values), biogenic opal and biomarkers (n-alkanes, fatty acids, sterols and amino acids) were determined in surface sediments from the Ob and Yenisei estuaries and the adjacent southern Kara Sea. Maximum TOC contents were determined in both estuaries, reaching up to 3 %. Relatively high C/N ratios around 10, light d13Corg values of -26.5 per mil (Yenisei) and -28 to -28.7 per mil (Ob), and maximum concentrations of long-chain n-alkanes of up to about 10 µg/g Sed clearly show the predominance of terrigenous organic matter in the sediments from the estuaries. Towards the open Kara Sea, all p arameters indicate a decrease in terrigenous organic carbon. Brassicasterol as well as the short-chain n-alkanes parallel this trend, suggesting that these biomarkers are probably also related to a terrigenous (fresh-water phytoplankton) source. Amino acid spectra show characteristic trends from the Yenisei Estuary to the open Kara Sea revealing increasing state of degradation. Sedimentary organic matter in the Yenisei Estuary is relatively less degraded compared to the Ob Estuary and the open Kara Sea.

Stable isotopic record of planktonic foraminifera of the Pacific Ocean

We determined the d18O and d13C of individual Globigerinoides ruber and Pulleniatina obliquiloculata from sediment traps located from 5°N to 12°S along 140°W in the Pacific Ocean to evaluate the effects of varying [CO3=] on shell d18O and d13C. Variations in the offset between shell d13C and d13CDIC (Dd13Cs-DIC) are attributed to differences in [CO3]2-, temperature, and shell size between sample sites. When Dd13Cs-DIC of G. ruber was corrected for variations in [CO3]2- using the experimental slope of Bijma et al. (1998), the residual Dd13Cs-DIC was correlated with mixed layer temperature (+0.10±0.04 per mil °C**-1). The slope of this temperature effect is consistent with experimental results. In P. obliquiloculata, Dd13Cs-DIC and temperature were strongly anticorrelated (?0.14±0.03 per mil C**-1). We are unable to separate the influences of [CO3]2- and temperature in this species without independent experimental data. Correcting for [CO3]2- variability on d18Os of G. ruber improves the accuracy of estimated sea surface temperatures.

Proglacial river dataset from the Akuliarusiarsuup Kuua River northern tributary, Southwest Greenland, 2008 - 2013, version 2.0

The dataset contains measurements of river stage and discharge for one sites along the Akuliarusiarsuup Kuua River's northern tributary, with 30 minute temporal resolution between June 2008 and August 2013 This river is a tributary to the Watson River discharging into Kangerlussuaq Fjord by the town of Kangerlussuaq, Southwest Greenland. Additional data of water temperature, air pressure are also provided. Compared to version 1.0 of the dataset, this dataset used a total of 36 in situ discharge observations collected between 2008 and 2012 to construct the rating curve. Furthermore, data of Station AK-004-001 between 2010-09-06T11:30 to 2010-09-07T13:30 have been removed from version 2.0 because these values were likely caused by backflow when a jokulhlaup from a large glacier dammed lake caused increased water levels in the downstreams lake. Thus, data measured at AK-004-001 between 2010-09-06T11:30 to 2010-09-07T13:30 are not representative for the AK-004 catchment.

Chemical and isotope compositions of thermal and surficial waters from the Chukotka Peninsula

Twenty three groups of thermomineral springs in the eastern Chukotka with discharge temperature from 2 to 97°C and mineralization from 1.47 to 37.14 g/l are studied and compared with surface freshwater from their localities. dD and d18O values in surface waters vary from -121.4 to -89.5 per mil and from -16.4 to -11.1 per mil, respectively, while respective values in thermomineral waters range from -134.2 to -92.5 per mil and from -17.6 to -10.5 per mil. dD value in surface waters decreases from the east to the west, i.e. toward interior areas of the peninsula. Hydrothermal springs most depleted in deuterium (dD < -120 per mil) are localized in the geodynamically active Kolyuchinskaya-Mechigmen Depression. According to the proposed formation model of Chukotka thermomineral waters their observed chemical and isotopic characteristics could result from mixing (in different proportions) of surface waters with the deep-sourced isotopically light mineralized component (dD = ca. -138 per mil, d18O = ca. -19 per mil, ? = from 9.5 to 14.7 g/l). The latter originates most likely from subpermafrost waters subjected to slight cryogenic metamorphism.

Authigenic carbonate of ODP SIte 104-643

Different generations of complex authigenic carbonates formed in siliceous muds (lithologic Unit IV) and hemipelagic clays (lithologic Unit V) of ODP Site 643, Leg 104 Norwegian Sea. The dominant phase in Unit IV is an early diagenetic Mn, Fe-calcite with a strong negative d13C ( -14 to -16 per mil) signature, and slightly negative d180 values. The strong negative d13C results from extensive incorporation of 12C-enriched CO2 derived from bacterial degradation of marine organic matter into early Mn, Fe - calcite cements. Concomitant framboidal pyrite precipitation and abundant SEM microtextures showing excellent preservation of delicate structures of fragile diatom valves by outpourings with early Mn-calcites strongly support their shallow burial formation before the onset of compaction. Later generations of authigenic mineralizations in lithologic Unit IV include minor amounts of a second generation of calcite with platy crystals, possibly precipitated along with opal-A dissolution, and finally opal-CT crystallization in deeper seated environments overgrowing earlier precipitates with films and lepispheres. The last mineralization is collophane (fluor apatite) forming amorphous aggregates and tiny hexagonal crystals. Authigenic mineral assemblages in lithologic Unit V consist of rhodochrosites, transitional rhodochrosite/manganosiderites, and apatite. A negative d13C ( -7.1 to -15.6 per mil) and a fluctuating d18O signal indicates that the micritic to sparitic rhodochrosites, transitional rhodochrosites/manganosiderites were formed at various burial depths. CO2 resulted from organic matter degradation in the lowermost sulfate reduction zone and from biogenic methane generation in the lowermost sediments, resulting in variable and negative d13C signals. The change in carbonate mineralogy reflects major compositional differences compared to sediments in Unit IV. Most prominent is an increase in altered ash as a primary sediment component and a sudden decrease of siliceous microfossils. Upward diffusion of cations, lowered salinities in pore waters, and elevated temperatures provide diagenetic environments favoring increased remobilization processes.

Benthic foraminifers, isotopes and varimax factors at DSDP Holes 72-517 and 72-518

Pliocene changes in the vertical water mass structure of the western South Atlantic are inferred from changes in benthic foraminiferal assemblages and stable isotopes from DSDP Holes 516A, 517, and 518. Factor analysis of 34 samples from Site 518 reveals three distinct benthic foraminiferal assemblages that have been associated with specific subsurface water masses in the modern ocean. These include a Nuttalides umbonifera assemblage (Factor 1) associated with Antarctic Bottom Water (AABW), a Globocassidulina subglobosa-Uvigerina peregrina assemblage (Factor 2) associated with Circumpolar Deep Water (CPDW), and an Oridorsalis umbonatus-Epistominella exigua assemblage associated with North Atlantic Deep Water (NADW). Bathymetric gradients in d13C between Holes 516A (1313 m), 517 (2963 m), and 518 (3944 m) are calculated whenever possible to monitor the degree of similarity and/or difference in the apparent oxygen utilization (AOU) of water masses located at these depths during the Pliocene. Changes in bathymetric d13C gradients coupled with benthic foraminiferal assemblages record fundamental changes in the vertical water mass structure of the Vema Channel during the Pliocene from 4.1 to 2.7 Ma. At Site 518, the interval from 4.1 to 3.6 Ma is dominated by the N. umbonifera (Factor 1) and O. umbonatus-E. exigua (Factor 3) assemblages. The d13C gradient between Holes 518 (3944 m) and 516A (1313 m) undergoes rapid oscillations during this interval though no permanent increase in the gradient is observed. However, d13C values at Site 518 are clearly lighter during this interval. These conditions may be related to increased bottom water activity associated with the re-establishment of the West Antarctic Ice Sheet in the late Gilbert Chron (-4.2 to 3.6 Ma) (Osborn et al., 1982). The interval from 3.6 to 3.2 Ma is marked by a dominance of the G. subglobosa-U. peregrina (Factor 2) assemblage and lack of a strong d13C gradient between Holes 518 (3944 m) and 516A (1313 m). We suggest that shallow circumpolar waters expanded to depths of a least 3944 m (Site 518) during this time. The most profound faunal and isotopic change occurs at 3.2 Ma, and is marked by dominance of the N. umbonifera (Factor 1) and O. umbonatus-E. exigua (Factor 3) assemblages, a 1.1 per mil enrichment in d18O, and a large negative increase in the d13C gradient between Holes 518 and 516A. These changes at Site 518 record the vertical displacement of circumpolar waters by AABW and NADW. This change in vertical water mass structure at 3.2 Ma was probably related to a global cooling event and/or final closure of the Central American seaway. A comparison of the present-day d13C structure of the Vema Channel with a reconstruction between 3.2 and 2.7 Ma indicates that circulation patterns during this late Pliocene interval were similar to those of the modern western South Atlantic.

CPI, d13C, Corg and diploptene from ODP Hole 169-1034B varved sediments

Saanich Inlet has been a highly productive fjord since the last glaciation. During ODP Leg 169S, nearly 70 m of Holocene sediments were recovered from Hole 1034 at the center of the inlet. The younger sediments are laminated, anaerobic, and rich in organic material (1-2.5 wt.% Corg), whereas the older sediments below 70 mbsf are non-laminated, aerobic, with glacio-marine characteristics and have a significantly lower organic matter content. This difference is also reflected in the changes of interstitial fluids, and in biomarker compositions and their carbon isotope signals. The bacterially-derived hopanoid 17alpha(H),21beta(H)-hop-22(29)-ene (diploptene) occurs in Saanich Inlet sediments throughout the Holocene but is not present in Pleistocene glacio-marine sediments. Its concentration increases after ~6000 years BP up to present time to about 70 µg/g Corg, whereas terrigenous biomarkers such as the n-alkane C31 are low throughout the Holocene (<51 µg/g Corg) and even slightly decrease to 36 µg/g Corg at the most recent time. The increasing concentrations of diploptene in sediments younger than ~6000 years BP separate a recent period of higher primary productivity, stronger anoxic bottom waters, and higher bacterial activity from an older period with lesser activity, heretofore undifferentiated. Carbon isotopic compositions of diploptene in the Holocene are between ~31.5 and ~39.6 per mil PDB after ~6000 years BP. These differences in the carbon isotopic record of diploptene probably reflect changes in microbial community structure of bacteria living at the oxic-anoxic interface of the overlying water column. The heavier isotope values are consistent with the activity of nitrifying bacteria and the lighter isotope values with that of aerobic methanotrophic bacteria. Therefore, intermediate delta13C values probably represent mixtures between the populations. In contrast, carbon isotopic compositions of n-C31 are roughly constant at ~31.4 ± 1.1 per mil PDB throughout the Holocene, indicating a uniform input from cuticular waxes of higher plants. Prior to ~6000 years BP, diploptene enriched in 13C of up to -26.3 per mil PDB is indicative of cyanobacteria living in the photic zone and suggests a period of lower primary productivity, more oxygenated bottom waters, and hence lower bacterial activity during the earliest Holocene.

Lagrangian back-tracing results for Kohnen station; output of time dependent numerical experiment with a 3D nested Antarctic ice sheet model

A nested ice flow model was developed for eastern Dronning Maud Land to assist with the dating and interpretation of the EDML deep ice core. The model consists of a high-resolution higher-order ice dynamic flow model that was nested into a comprehensive 3-D thermomechanical model of the whole Antarctic ice sheet. As the drill site is on a flank position the calculations specifically take into account the effects of horizontal advection as deeper ice in the core originated from higher inland. First the regional velocity field and ice sheet geometry is obtained from a forward experiment over the last 8 glacial cycles. The result is subsequently employed in a Lagrangian backtracing algorithm to provide particle paths back to their time and place of deposition. The procedure directly yields the depth-age distribution, surface conditions at particle origin, and a suite of relevant parameters such as initial annual layer thickness. This paper discusses the method and the main results of the experiment, including the ice core chronology, the non-climatic corrections needed to extract the climatic part of the signal, and the thinning function. The focus is on the upper 89% of the ice core (appr. 170 kyears) as the dating below that is increasingly less robust owing to the unknown value of the geothermal heat flux. It is found that the temperature biases resulting from variations of surface elevation are up to half of the magnitude of the climatic changes themselves.

Aboveground community and species-specific plant biomass from the Jena Experiment (Dominance Experiment, year 2006)

This data set contains aboveground community plant biomass (Sown plant community, Weed plant community, Dead plant material, and Unidentified plant material; all measured in biomass as dry weight) and species-specific biomass from the sown species of the dominance experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the dominance experiment, 206 grassland plots of 3.5 x 3.5 m were established from a pool of 9 plant species that can be dominant in semi-natural grassland communities of the study region. In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 3, 4, 6, and 9 species). Plots were maintained by bi-annual weeding and mowing. Aboveground community biomass was harvested twice in May and August 2006 on all experimental plots of the dominance experiment. This was done by clipping the vegetation at 3 cm above ground in two rectangles of 0.2 x 0.5 m per experimental plot. The location of these rectangles was assigned by random selection of coordinates within the central area of the plots (excluding an outer edge of 50cm). The positions of the rectangles within plots were identical for all plots. The harvested biomass was sorted into categories: individual species for the sown plant species, weed plant species (species not sown at the particular plot), detached dead plant material, and remaining plant material that could not be assigned to any category. All biomass was dried to constant weight (70°C, >= 48 h) and weighed. Sown plant community biomass was calculated as the sum of the biomass of the individual sown species. The mean of both samples per plot and the individual measurements are provided in the data file. Overall, analyses of the community biomass data have identified species richness and the presence of particular species as an important driver of a positive biodiversity-productivity relationship.

Hydrogen isotope composition of pore waters and interlayer water in sediments of ODP Leg 129 holes

Hydrogen isotope compositions have been measured on pore waters from sediments of Leg 129 sites in the Pigafetta and East Mariana basins (central western Pacific). Total water (pore + sorbed waters) contents and their dD have been analyzed for three samples that contain smectite but no zeolite so that sorbed water can be attributed to interlayer water. The H budget for pore and total waters implies that interlayer water is 20 per mil to 30 per mil depleted in D compared to pore water. Because the interlayer/total water molar ratio (0.25 to 0.5) in smectitic sediments is very high, interlayer water represents an important reservoir of D-depleted water in sediments. dD depth profiles for pore water at Sites 800 and 801 show breaks related to chert and radiolarite layers and are relatively vertical below. Above these chert units, pore waters are similar to modern seawater but below, they are between -10 per mil and -5.5 per mil. These values could represent little modified pre-Miocene seawater values, which were D-depleted because of the absence of polar caps, and were preserved from diffusive exchange with modern seawater by the relatively impermeable overlying chert layers. At Site 802, dD values of the pore waters show a decrease in the Miocene tuffs from 0 per mil values at the top to -8 per mil at 250 mbsf. Below, dD values are relatively uniform at about -8ë. Miocene tuffs are undergoing low water/rock alteration. A positive covariation of dD and Cl content of pore water in the tuffs suggests that the increase of dD values could result from secondary smectite formation. Low diffusive exchange coupled with D enrichment due to alteration of preglacial waters could explain the observed profile.

Aboveground community and species-specific plant biomass from the Jena Experiment (Dominance Experiment, year 2003)

This data set contains aboveground community plant biomass (Sown plant community, Weed plant community, and Dead plant material; all measured in biomass as dry weight) and species-specific biomass from the sown species of the dominance experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the dominance experiment, 206 grassland plots of 3.5 x 3.5 m were established from a pool of 9 plant species that can be dominant in semi-natural grassland communities of the study region. In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 3, 4, 6, and 9 species). Plots were maintained by bi-annual weeding and mowing. Aboveground community biomass was harvested twice in May and August 2003 on all experimental plots of the dominance experiment. This was done by clipping the vegetation at 3 cm above ground in two rectangles of 0.2 x 0.5 m per experimental plot. The location of these rectangles was assigned by random selection of coordinates within the central area of the plots (excluding an outer edge of 50cm). The positions of the rectangles within plots were identical for all plots. The harvested biomass was sorted into categories: individual species for the sown plant species, weed plant species (species not sown at the particular plot), detached dead plant material, and remaining plant material that could not be assigned to any category. All biomass was dried to constant weight (70°C, >= 48 h) and weighed. Sown plant community biomass was calculated as the sum of the biomass of the individual sown species. The mean of both samples per plot and the individual measurements are provided in the data file. Overall, analyses of the community biomass data have identified species richness and the presence of particular species as an important driver of a positive biodiversity-productivity relationship.

Chemical and isotopic composition of interstitial waters and hydrocarbon composition at ODP Site 184-1146

Bottom-simulating reflectors were observed beneath the southeastern slope of the Dongsha Islands in the South China Sea, raising the potential for the presence of gas hydrate in the area. We have analyzed the chemical and isotopic compositions of interstitial water, headspace gas, and authigenic siderite concretions from Site 1146. Geochemical anomalies, including a slight decrease of chlorine concentration in interstitial water, substantial increase of methane concentration in headspace gas, and 18O enrichment in the authigenic siderite concretion below 400 meters below seafloor are probably caused by the decomposition of gas hydrate. The low-chlorine pore fluids contain higher molecular-weight hydrocarbons and probably migrate to Site 1146 along faults or bedded planes.

Benthic foraminiferal faunas of Miocene to Holocene sediments of ODP Site 184-1143 from the southern South China Sea

Deep-sea benthic foraminiferal assemblages from Ocean Drilling Program (ODP) Site 1143 located in the southern South China Sea (SCS) were investigated to evaluate the relationship between faunal composition patterns and paleoceanographic changes during the last 6 million years (late Miocene to Holocene). We used multivariate statistics (correspondence analysis) to analyze carbon-flux-related changes in assemblage composition of benthic foraminifers. Additional proxies for carbon flux and deep-water ventilation include delta13C records of epifaunal Cibicidoides wuellerstorfi and infaunal Uvigerina peregrina var. dirupta and Melonis pompilioides, benthic foraminiferal accumulation rates (BFARs), diversity indices, and relative abundances of indicator species. We observe three significant benthic faunal changes in the southern South China Sea during the last 6 million years. Strong fluctuations in BFAR and relative abundance of productivity indicator species between glacial and interglacial stages after the mid-Pleistocene revolution (MPR) at approximately 0.9 Ma, indicating stronger seasonal carbon flux fluctuations, are accompanied by the extinction of such species as Stilostomella spp. Increases in carbon flux indicator species are coupled with an overall decrease in benthic foraminifer diversity around 3.0 Ma in the late Pliocene. This may indicate increasing carbon flux in a period of productivity maximum caused by enhanced offshore upwelling from intensified winter monsoon wind strength.

Oxygen and carbon isotope stratigraphy of ODP Holes 107-653A and 107-654A

Stable isotope analysis of two species (or groups of species) of planktonic foraminifers: Globigerinoides ruber (or G. obliquus and G. obliquus extremus) and Globigerina bulloides (or G. falconensis and G. obesa) from ODP Hole 653A and Site 654 in the Tyrrhenian basin, records the Pliocene-Pleistocene glacial history of the Northern Hemisphere. The overall increase in mean d18O values through the interval 4.6-0.08 Ma is 1.7 per mil for G. bulloides and 1.5 per mil for G. ruber. The time interval 3.1-2.5 Ma corresponds to an important phase of 18O enrichment for planktonic foraminifers. In this interval, glacial d18O values of both species G. bulloides and G. ruber increase by about l per mil, this increase being more progressive for G. ruber than for G. bulloides. The increase of interglacial d18O values is higher for G. bulloides (1.5 per mil) than for the Gruber group (1 per mil). These data suggest a more pronounced seasonal stratification of the water masses during interglacial phases. Large positive d18O fluctuations of increasing magnitude are also recorded at 2.25 and 2.15 Ma by G bulloides and appear to be diachronous with those of Site 606 in the Atlantic Ocean. Other events of increasing d18O values are recorded between 1.55 and 1.3 Ma, at 0.9 Ma, 0.8 Ma, and near 0.34 Ma. In the early Pliocene the d18O variability recorded by the planktonic species G. bulloides was higher in the Mediterranean than in the Atlantic at the same latitude. This suggests that important cyclic variations in the water budget of the Mediterranean occurred since that time. Step increases in the d18O variability are synchronous with those of the open ocean at 0.9 and 0.34 Ma. The higher variability as well as the higher amplitude of the peaks of 18O enrichment may be partly accounted for by increase of dryness over the Mediterranean area. In particular the high amplitude d18O fluctuations recorded between 3.1 and 2.1 Ma are correlated with the onset of a marked seasonal contrast and a summer dryness, revealed by pollen analyses. Strong fluctuations towards d13C values higher than modern ones are recorded by the G. ruber group species before 1.7 Ma and suggest a high production of phytoplankton. When such episodes of high primary production are correlated with episodes of decreasing 13C content of G. bulloides, they are interpreted as the consequence of a higher stratification of the upper water masses resulting itself from a marked seasonality. Such episodes occur between 4.6 and 4.05 Ma, 3.9 and 3.6 Ma, and 3.25 and 2.66 Ma. The interval 2.66-1.65 Ma corresponds to a weakening of the stratification of the upper water layers. This may be related to episodes of cooling and increasing dryness induced by the Northern Hemisphere Glaciations. The Pleistocene may have been a less productive period. The transition from highly productive to less productive surface waters also coincides with a new step increase in dryness and cooling, between 1.5 and 1.3 Ma. The comparison of the 13C records of G ruber and G. bulloides in fact suggests that a high vertical convection became a dominant feature after 2.6 Ma. Increases in the nutrient input and the stratification of the upper water masses may be suspected, however, during short episodes near 0.86 Ma (isotopic stage 25), 0.57-0.59 Ma (isotopic stage 16), 0.49 Ma (isotopic stage 13), 0.4-0.43 Ma (isotopic stage 11), and 0.22 and 0.26 Ma (part of isotopic stage 7 and transition 7/8). In fact, changes in the C02 balance within the different water masses of the Tyrrhenian basin as well as in the local primary production did not follow the general patterns of the open ocean.

Geochemistry of gas hydrates of DSDP Hole 84-570

During Deep Sea Drilling Project (DSDP) Leg 84 a core 1 m long and 6 cm in diameter of massive gas hydrate was unexpectedly recovered at Site 570 in upper slope sediment of the Middle America Trench offshore of Guatemala. This core contained only 5-7% sediment, the remainder being the solid hydrate composed of gas and water. Samples of the gas hydrate were decomposed under controlled conditions in a closed container maintained at 4°C. Gas pressure increased and asymptotically approached the equilibrium decomposition pressure for an ideal methane hydrate, CH4.5-3/4H2O, of 3930 kPa and approached to this pressure after each time gas was released, until the gas hydrate was completely decomposed. The gas evolved during hydrate decomposition was 99.4% methane, ~0.2% ethane, and ~0.4% CO2. Hydrocarbons from propane to heptane were also present, but in concentrations of less than 100 p.p.m. The carbon-isotopic composition of methane was -41 to -44 per mil, relative to PDB standard. The observed volumetric methane/water ratio was 64 or 67, which indicates that before it was stored and analyzed, the gas hydrate probably had lost methane. The sample material used in the experiments was likely a mixture of methane hydrate and water ice. Formation of this massive gas hydrate probably involved the following processes: (i) upward migration of gas and its accumulation in a zone where conditions favored the growth of gas hydrates, (ii) continued, unusually rapid biological generation of methane, and (iii) release of gas from water solution as pressure decreased due to sea level lowering and tectonic uplift.