Zircons, isotope ratios and element analyses from tonalite and oxide gabbro of the mid-ocean ridge from ODP Hole 176-735B

A limiting factor in the accuracy and precision of U/Pb zircon dates is accurate correction for initial disequilibrium in the 238U and 235U decay chains. The longest-lived-and therefore most abundant-intermediate daughter product in the 235U isotopic decay chain is 231Pa (T1/2 = 32.71 ka), and the partitioning behavior of Pa in zircon is not well constrained. Here we report high-precision thermal ionization mass spectrometry (TIMS) U-Pb zircon data from two samples from Ocean Drilling Program (ODP) Hole 735B, which show evidence for incorporation of excess 231Pa during zircon crystallization. The most precise analyses from the two samples have consistent Th-corrected 206Pb/238U dates with weighted means of 11.9325 ± 0.0039 Ma (n = 9) and 11.920 ± 0.011 Ma (n = 4), but distinctly older 207Pb/235U dates that vary from 12.330 ± 0.048 Ma to 12.140 ± 0.044 Ma and 12.03 ± 0.24 to 12.40 ± 0.27 Ma, respectively. If the excess 207Pb is due to variable initial excess 231Pa, calculated initial (231Pa)/(235U) activity ratios for the two samples range from 5.6 ± 1.0 to 9.6 ± 1.1 and 3.5 ± 5.2 to 11.4 ± 5.8. The data from the more precisely dated sample yields estimated DPazircon/DUzircon from 2.2-3.8 and 5.6-9.6, assuming (231Pa)/(235U) of the melt equal to the global average of recently erupted mid-ocean ridge basaltic glasses or secular equilibrium, respectively. High precision ID-TIMS analyses from nine additional samples from Hole 735B and nearby Hole 1105A suggest similar partitioning. The lower range of DPazircon/DUzircon is consistent with ion microprobe measurements of 231Pa in zircons from Holocene and Pleistocene rhyolitic eruptions (Schmitt (2007; doi:10.2138/am.2007.2449) and Schmitt (2011; doi:10.1146/annurev-earth-040610-133330)). The data suggest that 231Pa is preferentially incorporated during zircon crystallization over a range of magmatic compositions, and excess initial 231Pa may be more common in zircons than acknowledged. The degree of initial disequilibrium in the 235U decay chain suggested by the data from this study, and other recent high precision datasets, leads to resolvable discordance in high precision dates of Cenozoic to Mesozoic zircons. Minor discordance in zircons of this age may therefore reflect initial excess 231Pa and does not require either inheritance or Pb loss.

(Table 1) Maceral composition and organic carbon chemistry of ODP Leg 104 samples

The Cenozoic sediments sampled in ODP Leg 104 on the Vøring Plateau show a distinct variability of the total organic carbon content (TOC) and the accumulation rates of TOC. Based on the geochemical and organic-petrographic characterization of the sedimentary organic matter (OM), the allochthonous and autochthonous proportion of the OM could be quantified. The results clearly demonstrate that high TOC percentages and TOC accumulation rates in Cenozoic sediment sections display a generally high input of allochthonous organic matter. Oxidized and partly well-rounded organic particles built up the main portion of OM within the Miocene, TOC-rich sediments. The most probable source of this oxidized OM are reworked sediments from the Scandinavian shelf. Changes in the input of these organic particles are to some degree correlative with sea-level changes. The Cenozoic accumulation of autochthonous OM is low and does not reveal a clear variation during the Miocene and early Pliocene. In spite of a high accumulation rate of biogenic opal during the Early Miocene, the accumulation rate of autochthonous TOC is low. The autochthonous particle assemblage is dominated by relatively inert OM, like dinoflagellate cysts. This points to an intensive biological and/or early diagenetic degradation of the marine OM under well oxidized bottom water conditions during the last 23 Myr. Nevertheless, a continuation of marine OM degradation during later stages of diagenesis cannot be excluded. A prominent dominance of allochthonous OM over autochthonous is documented with the beginning of the Pliocene. At 2.45 Ma the episodic occurrence of ice-rafted, thermally mature OM reflects the onset of the glacial erosion of Mesozoic, coal and black shale bearing sediments on the Scandinavian and Barents Sea shelves. The first occurrence of these, in view of the actual burial depth, thermally overmature OM particles is, therefore, a marker for the beginning of the strong Scandinavian glaciation and the advance of the glacial front toward the shelves.

A refined Pliocene to early Pleistocene chronostratigraphic frame at ODP Hole 653A (West Mediterranean)

Two planktonic foraminiferal oxygen isotope records of ODP Hole 653A (Tyrrhenian Sea) are presented for the time period extending from approximately 0.8 to 3.0 Ma. Six, generally accepted, synchronous bioevents were used to precise the oxygen isotope chronology and to identify the oxygen isotope stages 22 down to 114. Subsequently, this oxygen isotope chronology was used to determine the synchronism or diachronism of various other biostratigraphic events with those recorded in the Singa and Ficarazzi land sections (Italy) and those in other DSDP/ODP sites. New results concern the diachronity of the FOD of the planktonic foraminiferal species N. atlantica, G.truncatulinoides truncatulinoides and G. inflata between ODP Hole 653A and the Italian landsections. Because many species entered the Mediterranean in short term fluxes, strongly related to the southward migration of cool North Atlantic surface waters, their time distribution through the Pliocene-Pleistocene generally corresponds to alternated intervals of presence and absence. This should explain most of the apparently diachronous appearances and disappearances. Alternating presence-absence patterns are of less importance for the various nannofossil events. The LOD of D. surculus occurs during the transition of stage 100 to 101 in both ODP Hole 653A and the Singa section, which is in perfect agreement with the disappearance of this species from the open ocean. The LOD of D. pentaradiatus in the Mediterranean occurs in stages 100-99, which seems to be consistent with the extinction of this species in the southern Hemisphere. G. oceanica, which corresponds to the 4 µm < Gephyrocapsa spp <5.5 µm is recorded in stages 65 to 64 at ODP Hole 653A. The Gephyrocapsa spp. >5.5 µm first occurred in stage 51 at Hole 653A, which fits within the uncertainty interval for this event stretching from stage 51 to 47 in the open ocean and seems therefore a useful tool for conventional biostratigraphy in the Mediterranean.

Stable isotope composition of carbonate components of Rhaetian shallow-water limestones of the Wombat Plateau

Stable oxygen- and carbon-isotope ratios of Rhaetian (upper Triassic) limestone samples from the Wombat Plateau, northwest Australia, were measured to explore possible diagenetic pathways that the material underwent after deposition in a shallow-water environment, before plateau submergence in the Early Cretaceous. Host sediment isotopic values cluster near typical marine carbonate values (d18O ranging from -2.57 per mil to +1.78 per mil and d13C, from +2.45 per mil to +4.01 per mil). Isotopic values of equant clear calcite lining or filling rock pores also plot in the field of marine cements (d18O = +1.59 per mil to -2.24 per mil and d13C = +4.25 per mil to +2.57 per mil), while isotopic values for neomorphic calcites replacing skeletal (megalodontid shell) carbonate material show a wider scatter of oxygen and carbon values, d18O ranging from +2.73 per milo to -6.2 per mil and d13C, from +5.04 per mil to +1.22 per mil. Selective dissolution of metastable carbonate phases (aragonite?) and neomorphic replacement of skeletal material probably occurred in a meteoric phreatic environment, although replacement products (inclusion-rich microspar, clear neomorphic spar, etc.) retained the original marine isotopic signature because transformation probably occurred in a closed system dominated by the composition of the dissolving phases (high rock/water ratio). The precipitation of late-stage equant (low-Mg?) calcite cement in the pores occurred in the presence of normal marine waters, probably in a deep-water environment, after plateau drowning. Covariance of d18O and d13C toward negative values indeed suggests influence of meteorically modified fluids. However, none of the samples shows negative carbon values, excluding the persistence of organic-rich soils on subaerial karstic surfaces (Caribbean-style diagenesis). Petrographical and geochemical data are consistent with the sedimentological evidence of plateau drowning in post-Rhaetian times and with a submarine origin of the >70-m.y.-long Jurassic hiatus.

In-situ Iron isotope measurements and mineral compositions from ODP Hole 206-1256D and IODP Hole 335-U1256D

In-situ Fe isotope measurements have been carried out to estimate the impact of the hydrothermal metamorphic overprint on the Fe isotopic composition of Fe-Ti-oxides and Fe-sulfides of the different lithologies of the drilled rocks from IODP Hole 1256D (eastern equatorial Pacific; 15 Ma crust formed at the East Pacific Rise). Most igneous rocks normally have a very restricted range in their 56Fe/54Fe ratio. In contrast, Fe isotope compositions of hot fluids (> 300 °C) from mid-ocean-ridge spreading centers define a narrow range that is shifted to lower delta 56Fe values by 0.2 per mil - 0.5 per mil as compared to igneous rocks. Therefore, it is expected that mineral phases that contain large amounts of Fe are especially affected by the interaction with a fluid that fractionates Fe isotopes during exsolution/precipitation of those minerals. We have used a femtosecond UV-Laser ablation system to determine mineral 56Fe/54Fe ratios of selected samples with a precision of < 0.1 per mil (2 sigma level) at micrometer-scale. We have found significant variations of the delta 56Fe (IRMM-014) values in the minerals between different samples as well as within samples and mineral grains. The overall observed scale of delta 56Fe (magnetite) in 1256D rocks ranges from - 0.12 to + 0.64 per mil, and of delta 56Fe (ilmenite) from - 0.77 to + 0.01 per mil. Pyrite in the lowermost sheeted dike section is clearly distinguishable from the other investigated lithological units, having positive delta 56Fe values between + 0.29 and + 0.56 per mil, whereas pyrite in the other samples has generally negative delta 56Fe values from - 1.10 to - 0.59 permil. One key observation is that the temperature dependent inter-mineral fractionations of Fe isotopes between magnetite and ilmenite are systematically shifted towards higher values when compared to theoretically expected values, while synthesized, well equilibrated magnetite-ilmenite pairs are compatible with the theoretical predictions. Theoretical considerations including beta-factors of different aqueous Fe-chlorides and Rayleigh-type fractionations in the presence of a hydrous, chlorine-bearing fluid can explain this observation. The disagreement between observed and theoretical equilibrium fractionation, the fact that magnetite, in contrast to ilmenite shows a slight downhole trend in the delta 56Fe values, and the observation of small scale heterogeneities within single mineral grains imply that a general re-equilibration of the magnetite-ilmenite pairs is overprinted by kinetic fractionation effects, caused by the interaction of magnetite/ilmenite with hydrothermal fluids penetrating the upper oceanic crust during cooling, or incomplete re-equilibration at low temperatures. Furthermore, the observation of significant small-scale variations in the 56Fe/54Fe ratios of single minerals in this study highlights the importance of high spatial-resolution-analyses of stable isotope ratios for further investigations.

Chemical characterization and quantification of the brown algal storage compound laminarin

In search of a meaningful stress indicator for Fucus vesiculosus we found that the often used quantitative determination procedures for the polysaccharide laminarin (beta-1,3-glucan) result in different kind of problems, uncertainties and limitations. This chemical long-term storage form of carbon enables perennial brown algae in seasonally fluctuating ecosystems to uncouple growth from photosynthesis. Because of this high ecological relevance a reliable and precise method for determination and quantification of laminarin is needed. Therefore, a simple, cold water extraction method coupled to a new quantitative liquid chromatography-mass spectrometrical method (LC-MS) was developed. Laminarin was determined in nine out of twelve brown algal species, and its expected typical molar mass distribution of 2000-7000 Da was confirmed. Furthermore, laminarin consisted of a complex mixture of different chemical forms, since fifteen chemical laminarin species with distinct molecular weights were measured in nine species of brown algae. Laminarin concentrations in the algal tissues ranged from 0.03 to 0.86% dry weight (DW). The direct chemical characterization and quantification of laminarin by LC-MS represents a powerful method to verify the biochemical and ecological importance of laminarin for brown algae. Single individuals of Laminaria hyperborea, L. digitata, Saccharina latissima, F. serratus, F. vesiculosus, F. spiralis, Himanthalia elongata, Cystoseira tamariscifolia, Pelvetia canaliculata, Ascophyllum nodosum, Halidrys siliquosa and Dictyota dichotoma were collected in fall (18.11.2013) during spring low tide from the shore of Finavarra, Co. Clare, west coast of Ireland (53° 09' 25'' N, 09° 06' 58'' W). After sampling, the different algae were immediately transported to the lab, lyophilized and sent to the University of Rostock. Laminarin was extracted with cold ultrapure water from the algal samples. Before extraction they were ground to < 1 mm grain size with an analytical mill (Ika MF 10 Basic). The algal material (approx. 1.5 g DW) was extracted in ultrapure water (8 mL) on a shaker (250 rpm) for 5 h. After the addition of surplus ultrapure water (4 mL) and shaking manually, 1 mL of the sample was filter centrifuged (45 µm) at 14,000 rpm (Hettich Mikro 22 R). The slightly viscous supernatant was free of suspended material and converted into a microvial (300 µL) for further analysis. The extracts were analyzed using liquid chromatography-mass spectrometry (LC-MS) analysis (LTQ Velos Pro ion trap spectrometer with Accela HPLC, Thermo Scientific). Laminarin species were separated on a KinetexTM column (2.6 µm C18, 150 x 3 mm). The mobile phase was 90 % ultrapure water and 10 % acetonitrile, run isocratically at a flow rate of 0.2 mL min-1. MS was working in ESI negative ion mode in a mass range of 100 - 4000 amu. Glucose contents were determined after extraction using high-performance liquid chromatography (HPLC). Extracted samples were analyzed in an HPLC (SmartLine, Knauer GmbH) equipped with a SUPELCOGELTM Ca column (30 x 7,8 mm without preColumn) and RI-detector (S2300 PDA S2800). Water was used as eluent at a flow rate of 0.8 mL min-1 at 75 °C. Glucose was quantified by comparison of the retention time and peak area with standard solutions using ChromGate software. Mannitol was extracted from three subsamples of 10-20 mg powdered alga material (L. hyperborea, L. digitata, S. latissima, F. serratus, F. vesiculosus, F. spiralis, H. elongata, P. canaliculata, A. nodosum, H. siliquosa) and quantified, following the HPLC method described by Karsten et al. (1991). For analyzing carbon and nitrogen contents, dried algal material was ground to powder and three subsamples of 2 mg from each alga thalli were loaded and packed into tin cartridges (6×6×12 mm). The packages were combusted at 950 °C and the absolute contents of C and N were automatically quantified in an elemental analyzer (Elementar Vario EL III, Germany) using acetanilide as standard according to Verardo et al. (1990).

Carbon chemistry of ODP Leg 105 sites

The quantity and quality of organic carbon of Eocene to Holocene sediments from ODP Sites 645, 646, and 647 were investigated to reconstruct depositional environments. Results were based on organic-carbon and nitrogen determinations, Rock-Eval pyrolysis, and kerogen microscopy. The sediments at Site 645 in Baffin Bay are characterized by relatively high organic-carbon values, most of which range from 0.5% to almost 3%, with maximum values in the middle Miocene. Distinct maxima of organic-carbon accumulation rates occur between 18 and 12.5 Ma and between 3.4 and 0 Ma. At Sites 646 and 647 in the Labrador Sea, organic-carbon contents vary between 0.1% and 0.75%. Cyclic 'Milankovitch-type' changes in organic-carbon deposition imply climate-controlled mechanisms that cause these fluctuations. The composition of organic matter at Site 645 is dominated by terrigenous components throughout the entire sediment sequence. An increased content of marine organic carbon was recorded only in the late-middle Miocene. At Sites 646 and 647, the origin of the organic matter most probably is marine. Oceanic paleoproductivity values were estimated, based on the amount of marine organic carbon. During most of the Neogene time interval at Site 645, productivity was low, i.e., similar or less than that measured in Baffin Bay today. Higher values of up to 150 (200) gC/m**2/y may have occurred only in the Miocene. At Sites 646 and 647, mean paleoproductivity values vary between 90 and 170 gC/m**2/y; i.e., these are also similar to those measured in the Labrador Sea today. Lower values of 40 to 70 gC/m**2/y were estimated for the early Eocene and (middle) Miocene.

Petrology and geochemistry at DSDP Site 59-448

This chemical and petrologic study of rocks from Site 448 on the Palau-Kyushu Ridge is designed to answer some fundamental questions concerning the volcanic origin of remnant island arcs. According to the reconstruction of the Western Pacific prior to about 45 m.y. ago (Hilde et al., 1977), the site of the Palau-Kyushu Ridge was a major transform fault. From a synthesis of existing geological and geophysical data (R. Scott et al., this volume), it appears that the ridge originated by subduction of the Pacific plate under the West Philippine Basin. Thus the Palau-Kyushu Ridge should be a prime example of both initial volcanism of an incipient arc formed by interaction of oceanic lithospheric plates and remnant-arc volcanic evolution. The Palau-Kyushu Ridge was an active island arc from about 42 to 30 m.y. ago, after which initiation of back-arc spreading formed the Parece Vela Basin (R. Scott et al., this volume; Karig, 1975a). This spreading left the western portion of the ridge as a remnant arc that separates the West Philippine Basin from the Parece Vela Basin. In spite of numerous oceanographic expeditions to the Philippine Sea, including the two previous DSDP Legs 6 and 31 (Fischer, Heezen et al., 1971; Karig, Ingle et al., 1975), and even though the origins of inter-arc basins have been linked by various hypotheses to that of remnant island arcs (Karig, 1971, 1972, 1975a, and 1975b; Gill, 1976; Uyeda and Ben-Avraham, 1972; Hilde et al., 1977), very little hard data are available on inactive remnant arcs.

Chemistry of gabbroic rocks of ODP Hole 118-735B

We present results of a microprobe investigation of fresh and least-deformed and metamorphosed gabbroic rocks from Leg 118, Hole 735B, drilled on the east side of the Atlantis II Fracture Zone, Southwest Indian Ridge. This rock collection comprises cumulates ranging from troctolites to olivine-gabbro and olivine-gabbronorite to ilmenite-rich ferrogabbros and ferrogabbronorites. As expected, the mineral chemistry is variable and considerably expands the usual oceanic reference spectrum. Olivine, plagioclase, and clinopyroxene are present in all the studied samples. Orthopyroxene and ilmenite, although not rare, are not ubiquitous. Olivine compositions range from Fo85 to Fo30, while plagioclase compositions vary from An70 to An27. Mg/(Mg + Fe2+) of clinopyroxene (mostly diopside to augite) varies from 0.88 to 0.54. Mg/(Mg + Fe2+) of orthopyroxene varies from 0.84 to 0.50. These minerals are not significantly zoned. All mineralogical data indicate that fractional crystallization is an important factor for the formation of cumulates. However, sharp contacts, interpreted as layering boundaries or intrusion margins, suggest polycyclic fractionation of several magma batches of limited volumes. Calculated compositions of magmas in equilibrium with the most magnesian mineral samples at the bottom of the hole represent fractionated liquids through separation of olivine, plagioclase, and clinopyroxene at moderate to low pressures (less than 9 kb). Crystallization of orthopyroxene and ilmenite occurs in the most differentiated liquids. Mixing of magmas having various compositions before entering the cumulate zone is another mechanism necessary to explain extremely differentiated iron-rich gabbros formed in this slow-spreading ridge environment.

Consolidation properties and strength characteristics of ODP Site 204-1244 sediments

Eight whole-core samples from Ocean Drilling Program Site 1244, Hydrate Ridge, Cascadia continental margin, were provided to Massachusetts Institute of Technology (Cambridge, Massachusetts, USA) for geotechnical characterization. The samples were collected from depths ranging from 5 to 136 meters below seafloor (mbsf). Seven of the eight whole-core samples were located within the gas hydrate stability zone, whereas the eighth sample was located in the free gas zone. Atterberg limits testing showed that the average liquid limit of the soil is 81% and the average plastic limit is 38%, giving an average plasticity index of 43%. The liquid limit is sensitive to oven drying, shown by a drop in liquid limit to 64% when tests were performed on an oven-dried sample. Loss on ignition averages 5.45 wt%. Constant rate of strain consolidation (CRSC) tests were performed to obtain the compression characteristics of the soil, as well as to determine the stress history of the site. CRSC tests also provided hydraulic conductivity and coefficient of consolidation characteristics for these sediments. The compression ratio (Cc) ranges from 0.340 to 0.704 (average = 0.568). Cc is fairly constant to a depth of 79 mbsf, after which Cc decreases downhole. The recompression ratio (Cr) ranges from 0.035 to 0.064 (average = 0.052). Cr is constant throughout the depth range. In situ hydraulic conductivity varies between 1.5 x 10**-7 and 3 x 10**-8 cm/s and shows no trend with depth. Ko-consolidated undrained compression/extension (CKoUC/E) tests were also performed to determine the peak undrained shear strength, stress-strain curve, and friction angle. The normalized undrained strength ranges from 0.29 to 0.35. The friction angle ranges from 27 to 37. Because of the limited amount of soil, CRSC and CKoUC/E tests were also conducted on resedimented specimens.

Zirkon fission track ages of for middle Pleistocene Rangitawa Tephra, New Zealand

Rangitawa Tephra is an important stratigraphic marker in mid-Pleistocene marine and terrestrial sequences in New Zealand and adjacent ocean basins. Zircon fission track ages (ZFTA) on Rangitawa Tephra from five sites in the southern North Island yield mean site ages in the range 0.34 to 0.40 Ma with a weighted mean of 0.35 + 0.04 Ma (1 sigma). On the basis of glass shard major-element chemistry, ferromagnesian mineralogy, ZFTA and similarity of paleomagnetic dates of proposed tephra correlalives in deep-sea cores, it is concluded that Rangitawa Tephra represents a major eruptive event in the Taupo Volcanic Zone most probably associated with eruption of the Whakamaru-group ignimbrites (0.35 0.39 Ma) or less likely the Paeroa Range Group Ignimbrites (0.36 -0.38 Ma). Pollen analyses from two onshore sites, together with regional loess stratigraphy, show that Rangitawa Tephra was erupted during a glacial period. The ZFTA and previously reported oxygen isotope data from DSDP Site 594 indicate that Rangitawa Tephra was erupted near the end of oxygen isotope stage 10.

(Table 1) Sea ice and snow characteristics and heat fluxes observed during R/V Aurora Australis cruise to East Antarctica in September/October 2007

The properties of snow on East Antarctic sea ice off Wilkes Land were examined during the Sea Ice Physics and Ecosystem Experiment (SIPEX) in late winter of 2007, focusing on the interaction with sea ice. This observation includes 11 transect lines for the measurement of ice thickness, freeboard, and snow depth, 50 snow pits on 13 ice floes, and diurnal variation of surface heat flux on three ice floes. The detailed profiling of topography along the transects and the d18O, salinity, and density datasets of snow made it possible to examine the snow-sea-ice interaction quantitatively for the first time in this area. In general, the snow displayed significant heterogeneity in types, thickness (mean: 0.14 +- 0.13 m), and density (325 +- 38 kg/m**3), as reported in other East Antarctic regions. High salinity was confined to the lowest 0.1 m. Salinity and d18O data within this layer revealed that saline water originated from the surface brine of sea ice in 20% of the total sites and from seawater in 80%. From the vertical profiles of snow density, bulk thermal conductivity of snow was estimated as 0.15 W/K/m on average, only half of the value used for numerical sea-ice models. Although the upward heat flux within snow estimated with this value was significantly lower than that within ice, it turned out that a higher value of thermal conductivity (0.3 to 0.4 W/K/m) is preferable for estimating ice growth amount in current numerical models. Diurnal measurements showed that upward conductive heat flux within the snow and net long-wave radiation at the surface seem to play important roles in the formation of snow ice from slush. The detailed surface topography allowed us to compare the air-ice drag coefficients of ice and snow surfaces under neutral conditions, and to examine the possibility of the retrieval of ice thickness distribution from satellite remote sensing. It was found that overall snow cover works to enhance the surface roughness of sea ice rather than moderate it, and increases the drag coefficient by about 10%. As for thickness retrieval, mean ice thickness had a higher correlation with ice surface roughness than mean freeboard or surface elevation, which indicates the potential usefulness of satellite L-band SAR in estimating the ice thickness distribution in the seasonal sea-ice zone.

(Table 1) Stable carbon and nitrogen isotopic ratios of potential prey species of bearded seals (Erignathus barbatus), Svalbard

Changing patterns of sea-ice distribution and extent have measurable effects on polar marine systems. Beyond the obvious impacts of key-habitat loss, it is unclear how such changes will influence ice-associated marine mammals in part because of the logistical difficulties of studying foraging behaviour or other aspects of the ecology of large, mobile animals at sea during the polar winter. This study investigated the diet of pregnant bearded seals (Erignathus barbatus) during three spring breeding periods (2005, 2006 and 2007) with markedly contrasting ice conditions in Svalbard using stable isotopes (d13C and d15N) measured in whiskers collected from their newborn pups. The d15N values in the whiskers of individual seals ranged from 11.95 to 17.45 per mil, spanning almost 2 full trophic levels. Some seals were clearly dietary specialists, despite the species being characterised overall as a generalist predator. This may buffer bearded seal populations from the changes in prey distributions lower in the marine food web which seems to accompany continued changes in temperature and ice cover. Comparisons with isotopic signatures of known prey, suggested that benthic gastropods and decapods were the most common prey. Bayesian isotopic mixing models indicated that diet varied considerably among years. In the year with most fast-ice (2005), the seals had the greatest proportion of pelagic fish and lowest benthic invertebrate content, and during the year with the least ice (2006), the seals ate more benthic invertebrates and less pelagic fish. This suggests that the seals fed further offshore in years with greater ice cover, but moved in to the fjords when ice-cover was minimal, giving them access to different types of prey. Long-term trends of sea ice decline, earlier ice melt, and increased water temperatures in the Arctic are likely to have ecosystem-wide effects, including impacts on the forage bases of pagophilic seals.

Water, bottom deposits, and macrobenthos in the south part of the East Siberian Sea in September 2003

Macrobenthos biomass and bottom biocoenoses were studied in the sublittoral zone of the southern East Siberian Sea. The macrobenthos is characterized by relatively high abundance (from 30 to 2680 #/m**2), biomass (from 0.25 to 578.8 g/m**2), and diversity (83 species in total). Lateral distribution of macrobenthos biomass correlates with a substrate type and salinity and is substantially higher in areas washed by the Arctic water mass than in estuaries with mixed fresh and Arctic waters and shows a tendency to decreasing in the convergence zone of different water masses. The highest macrobenthos biomass is observed in cores of water masses in the Long Strait area and in the eastern part of the sea.

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.