Distribution of grain size and clay minerals in surface sediments of the Kara Sea (Fig 4, 5)

In this paper, we summarize data on terrigenous sediment supply in the Kara Sea and its accumulation and spatial and temporal variability during Holocene times. Sedimentological, organic-geochemical, and micropaleontological proxies determined in surface sediments allow to characterize the modern (riverine) terrigenous sediment input. AMS-14C dated sediment cores from the Ob and Yenisei estuaries and the adjacent inner Kara Sea were investigated to determine the terrigenous sediment fluxes and their relationship to paleoenvironmental changes. The variability of sediment fluxes during Holocene times is related to the post-glacial sea-level rise and changes in river discharge and coastal erosion input. Whereas during the late/middle Holocene most of the terrigenous sediments were deposited in the estuaries and the areas directly off the estuaries, huge amounts of sediments accumulated on the Kara Sea shelf farther north during the early Holocene before about 9 cal kyr BP. The maximum accumulation at that time is related to the lowered sea level, increased coastal erosion, and increased river discharge. Based on sediment thickness charts, echograph profiles and sediment core data, we estimate an average Holocene (0-11 cal kyr BP) annual accumulation of 194,106 t/yr of total sediment for the whole Kara Sea. Based on late Holocene (modern) sediment accumulation in the estuaries, probably 12,106 t/yr of riverine suspended matter (i.e. about 30% of the input) may escape the marginal filter on a geological time scale and is transported onto the open Kara Sea shelf. The high-resolution magnetic susceptibility record of a Yenisei core suggests a short-term variability in Siberian climate and river discharge on a frequency of 300-700 yr. This variability may reflect natural cyclic climate variations to be seen in context with the interannual and interdecadal environmental changes recorded in the High Northern Latitudes over the last decades, such as the NAO/AO pattern. A major decrease in MS values starting near 2.5 cal kyr BP, being more pronounced during the last about 2 cal kyr BP, correlates with a cooling trend over Greenland as indicated in the GISP-2 Ice Core, extended sea-ice cover in the North Atlantic, and advances of glaciers in western Norway. Our still preliminary interpretation of the MS variability has to be proven by further MS records from additional cores as well as other high-resolution multi-proxy Arctic climate records.

Tab. 1: Rates of advance of the frontal push-moraines of 19 lobes in front of an approx. 4.5 km long margin of the Kötlujökull

In the last years masses of ice, about 5 km long, have been protruding from the lowest part of an advancing glacier margin of the Kötlujökull in Southern Iceland. In the summer of 1983, they appeared as sediment-covered lobes, 10-60 m long, bordering the glacier rnargin like agarland. 1 to 3 push-rnoraines without ice core, rnostly sickle-shaped, occured first in the frontal parts of the lobes: behind thern came several ice-cored moraines with heights of up to several metres. The active ice in front of the precipice of the glacier is called the "glacier-foot" in this paper. The digging out of 9 lobes and the measuring of the advance of 19 lobes showed that in most cases this glacierfoot had split up at its distal end into several plate- or stem-shaped pieces of ice which were situated one upon the other, separated by moraine deposits and proceeding irregularly into the foreland at the rate of several mm/h, The sometimes different rate of advance in the same lobe and different rates of advanee in adjoining lobes (some being entirely inactive) point to a type of rnovement which is independent of the general advance of the glacier. Research in the winter of 1983/84 showed less activity in 3 examined lobes, but the activity had not ceased. The advancement of the lower parts of the glacier-foot into and across the sands of the foreland implies the following genesis of pushmoraines: Shoving off a plate of sand, folding it and pushing it over the foreland at average rates of up to 7,2 mm/h, according to the investigations in thc summer of 1983. At a certain stage of the folding process, new folds begin to develop in front of the old, and the old folds are shifted onto the backslope of thc folds in front of them until they are completely unired. In this way, "püe-moraines" arise, which become higher and higher. They include two or more folds declining towards the glacier. Systems of small moraines presumably of the same genesis occur on old moraine areas in front of the Kötlujökull. The possible cause of formation of a glacier-foot is discussed, and the moraines of the Kötlujökull are compared with certain pleistocene push-moraines.

(Table 4+5, Page 290) Distribution of Mn, Fe, Cu. Pb, Zn, Ni and Co in single manganese nodules

Chemical analyses of manganese nodules from the Central Pacific Basin show that their chemical composition varies regionally, although that of the associated sediments is markedly uniform throughout the basin. Mn content varies from 16 to 32% in average. Its higher value is generally found in nodules from siliceous clay and a few from deep-sea clay. Fe content tends to enrich in nodules from deep-sea clay area. Most manganese nodules, except those from deep-sea clay, are remarkably depleted in Fe compared with ones from the other Pacific regions. Mostly, Cu and Ni contents exceed 1% in nodules from siliceous clay, and decrease towards the northwest of the basin where deep-sea clay is distributed. The inter-element relationship between manganese nodules and associated sediments suggests that the mechanism of incorporation of major and minor elements in nodules is apparently different from that of the associated sediments. This finding seems to provide a new interpretation on the problem why manganese nodules having low accumulation rate are not buried by the associated sediments with greater sedimentation rate and then occur on sediment-seawater interface.

Sulfur contents and S, C and O isotopic compositions in serpentinized peridotites at ODP Site 153-920

The opaque mineralogy and the contents and isotope compositions of sulfur in serpentinized peridotites from the MARK (Mid-Atlantic Ridge, Kane Fracture Zone) area were examined to understand the conditions of serpentinization and evaluate this process as a sink for seawater sulfur. The serpentinites contain a sulfur-rich secondary mineral assemblage and have high sulfur contents (up to 1 wt.%) and elevated d34S_sulfide (3.7 to 12.7?). Geochemical reaction modeling indicates that seawater-peridotite interaction at 300 to 400°C alone cannot account for both the high sulfur contents and high d34S_sulfide. These require a multistage reaction with leaching of sulfide from subjacent gabbro during higher temperature (~400°C) reactions with seawater and subsequent deposition of sulfide during serpentinization of peridotite at ~300°C. Serpentinization produces highly reducing conditions and significant amounts of H2 and results in the partial reduction of seawater carbonate to methane. The latter is documented by formation of carbonate veins enriched in 13C (up to 4.5?) at temperatures above 250°C. Although different processes produce variable sulfur isotope effects in other oceanic serpentinites, sulfur is consistently added to abyssal peridotites during serpentinization. Data for serpentinites drilled and dredged from oceanic crust and from ophiolites indicate that oceanic peridotites are a sink for up to 0.4 to 6.0 mln ton seawater S per year. This is comparable to sulfur exchange that occurs in hydrothermal systems in mafic oceanic crust at midocean ridges and on ridge flanks and amounts to 2 to 30% of the riverine sulfate source and sedimentary sulfide sink in the oceans. The high concentrations and modified isotope compositions of sulfur in serpentinites could be important for mantle metasomatism during subduction of crust generated at slow spreading rates.

EPICA Dome C Ice Core Timescales EDC3

The EPICA (European Project for Ice Coring in Antarctica) Dome C drilling in East Antarctica has now been completed to a depth of 3260 m, at only a few meters above bedrock. Here we present the new EDC3 chronology, which is based on the use of 1) a snow accumulation and mechanical flow model, and 2) a set of independent age markers along the core. These are obtained by pattern matching of recorded parameters to either absolutely dated paleoclimatic records, or to insolation variations. We show that this new time scale is in excellent agreement with the Dome Fuji and Vostok ice core time scales back to 100 kyr within 1 kyr. Discrepancies larger than 3 kyr arise during MIS 5.4, 5.5 and 6, which points to anomalies in either snow accumulation or mechanical flow during these time periods. We estimate that EDC3 gives accurate event durations within 20% (2 sigma) back to MIS11 and accurate absolute ages with a maximum uncertainty of 6 kyr back to 800 kyr.

Measurements of seawater and aerosol particles during POLARSTERN cruise ANT-XXVII/4

An analytical method for the determination of the alpha dicarbonyls glyoxal (GLY) and methylglyoxal (MGLY) from seawater and marine aerosol particles is presented. The method is based on derivatization with o-(2,3,4,5,6-Pentafluorobenzyl)-hydroxylamine (PFBHA) reagent, solvent extraction and GC-MS (SIM) analysis. The method showed good precision (RSD < 10%), sensitivity (detection limits in the low ng/l range), and accuracy (good agreement between external calibration and standard addition). The method was applied to determine GLY and MGLY in oceanic water sampled during the Polarstern cruise ANT XXVII/4 from Capetown to Bremerhaven in spring 2011. GLY and MGLY were determined in the sea surface microlayer (SML) of the ocean and corresponding bulk water (BW) with average concentrations of 228 ng/l (GLY) and 196 ng/l (MGLY). The results show a significant enrichment (factor of 4) of GLY and MGLY in the SML. Furthermore, marine aerosol particles (PM1) were sampled during the cruise and analyzed for GLY (average concentration 0.19 ng/m**3) and MGLY (average concentration 0.15 ng/m**3). On aerosol particles, both carbonyls show a very good correlation with oxalate, supporting the idea of a secondary formation of oxalic acid via GLY and MGLY. Concentrations of GLY and MGLY in seawater and on aerosol particles were correlated to environmental parameters such as global radiation, temperature, distance to the coastline and biological activity. There are slight hints for a photochemical production of GLY and MGLY in the SML (significant enrichment in the SML, higher enrichment at higher temperature). However, a clear connection of GLY and MGLY to global radiation as well as to biological activity cannot be concluded from the data. A slight correlation between GLY and MGLY in the SML and in aerosol particles could be a hint for interactions, in particular of GLY, between seawater and the atmosphere.

Bulk geochemistry and grain-size composition of surface sediments from the SW Atlantic

Surface sediments from the South American continental margin surrounding tbe Argentine Basin were studied with respect to bulk geochemistry (Caeo) and C ) and grain-size composition (sand/silt/clay relation and terrigenous silt grain-size distribution). The grain-size distributions of the terrigenous silt fraction were unmixed into three end members (EMs), using an end-member modelling algorithm. Three unimodal EMs appear to satisfactorily explain the variations in the data set of the grain-size distributions ofterrigenous silt. The EMs are related to sediment supply by rivers, downslope transport, winnowing, dispersal and re-deposition by currents. The bulk geochemical composition was used to trace the distribution of prominent water masses within the vertical profile. The sediments of the eastern South American continental margin are generally divided into a coarse-grained and carbonate-depleted southwestern part, and a finer-grained and carbonate-rich northeastern part. The transition of both environments is located at the position of the Brazil Malvinas Confluence (BMC). The sediments below the confluence mixing zone of the Malvinas and Brazil Currents and its extensions are characterised by high concentrations of organic carbon, low carbonate contents and high proportions of the intennediate grain-size end member. Tracing these properties, the BMC emerges as a distinct north-south striking feature centered at 52-54°W crossing the continental margin diagonally. Adjacent to this prominent feature in the southwest, the direct detrital sediment discharge of the Rio de la Plata is clearly recognised by a downslope tongue of sand and high proportions of the coarsest EM. A similar coarse grain-size composition extends further south along the continental slope. However, it displays bener sorting due to intense winnowing by the vigorous Malvinas Current. Fine-grained sedimentary deposition zones are located at the southwestern deeper part of the Rio Grande Rise and the southern abyssal Brazil Basin, both within the AABW domain. Less conspicuous winnowing/accumulation panerns are indicated north of the La Plata within the NADW level according to the continental margin topography. We demonstrate that combined bulk geochemical and grain-size properties of surface sediments, unmixed with an end-member algorithm, provide a powerful tool to reconstruct the complex interplay of sedimentology and oceanography along a time slice.

C and H geochemistry of altered oceanic crus of ODP/IODP Hole 1256D

Carbon and hydrogen concentrations and isotopic compositions were measured in 19 samples from altered oceanic crust cored in ODP/IODP Hole 1256D through lavas, dikes down to the gabbroic rocks. Bulk water content varies from 0.32 to 2.14 wt% with dD values from -64per mil to -25per mil. All samples are enriched in water relative to fresh basalts. The dD values are interpreted in terms of mixing between magmatic water and another source that can be either secondary hydrous minerals and/or H contained in organic compounds such as hydrocarbons. Total CO2, extracted by step-heating technique, ranges between 564 and 2823 ppm with d13C values from -14.9per mil to -26.6per mil. As for water, these altered samples are enriched in carbon relative to fresh basalts. The carbon isotope compositions are interpreted in terms of a mixing between two components: (1) a carbonate with d13C = -4.5per mil and (2) an organic compound with d13C = -26.6per mil. A mixing model calculation indicates that, for most samples (17 of 19), more than 75% of the total C occurs as organic compounds while carbonates represent less than 25%. This result is also supported by independent estimates of carbonate content from CO2 yield after H3PO4 attack. A comparison between the carbon concentration in our samples, seawater DIC (Dissolved Inorganic Carbon) and DOC (Dissolved Organic Carbon), and hydrothermal fluids suggests that CO2 degassed from magmatic reservoirs is the main source of organic C addition to the crust during the alteration process. A reduction step of dissolved CO2 is thus required, and can be either biologically mediated or not. Abiotic processes are necessary for the deeper part of the crust (>1000 mbsf) because alteration temperatures are greater than any hyperthermophilic living organism (i.e. T > 110 °C). Even if not required, we cannot rule out the contribution of microbial activity in the low-temperature alteration zones. We propose a two-step model for carbon cycling during crustal alteration: (1) when "fresh" oceanic crust forms at or close to ridge axis, alteration starts with hot hydrothermal fluids enriched in magmatic CO2, leading to the formation of organic compounds during Fischer-Tropsch-type reactions; (2) when the crust moves away from the ridge axis, these interactions with hot hydrothermal fluids decrease and are replaced by seawater interactions with carbonate precipitation in fractures. Taking into account this organic carbon, we estimate C isotope composition of mean altered oceanic crust at ? -4.7per mil, similar to the d13C of the C degassed from the mantle at ridge axis, and discuss the global carbon budget. The total flux of C stored in the altered oceanic crust, as carbonate and organic compound, is 2.9 ± 0.4 * 10**12 molC/yr.