Mineralogy of Hawaiian Arch sediments

The mineralogy of both bulk- and clay-sized (<2 µm) fractions of sediments from Holes 842A and 842B of Ocean Drilling Program Leg 136 was determined by X-ray diffraction. The sediments consist of a combination of terrigenous (quartz, plagioclase, smectite, illite, kaolinite, and chlorite), volcaniclastic (augite, plagioclase, and volcanic glass), and diagenetic minerals (smectite, phillipsite, clinoptilolite, and opal-CT). Although biogenic silica (radiolarians and diatoms) is common in near-seafloor (<10 mbsf) sediments, biogenic calcite is rare. Variations with depth in abundances of the terrigenous minerals reflect temporal changes in the flux of eolian material to the site. Volcanogenic material derived from the Hawaiian Islands is present in lithologic Unit 1 (0-19.9 meters below seafloor) both as discrete layers and as finely disseminated silt- and clay-sized material. Volcanic glass is present only in the upper 10 m of the sediment column. In Unit 2 (19.9-35.7 mbsf), increased smectite and zeolite abundances with depth as well as indurated, zeolite-rich layers are thought to be the alteration products of volcanogenic material. The source of this older (late Oligocene to middle Miocene) volcanogenic detritus may be continental volcanism. Microfabrics imaged using back-scattered electron imaging reflect the effects of compaction and diagenesis on sediment porosity and matrix structure. As porosity decreases during burial, the matrix changes from an open, floc-like fabric, to an interlocking network of clay mineral domains, and finally to a dense intergrowth of clay minerals and zeolites. Despite the substantial changes in sediment microfabric and mineralogy, correlations between physical and acoustic properties and mineralogy are weak or absent. The sediment has maintained high porosity (>70%), and water content appears to dominate the sediment's physical character and acoustic response.

Radiolarian assemblages of the late Neogene North Pacific

Radiolarian census and abundance data were collected from three deep-sea cores drilled by the Ocean Drilling Program Sites 884, 887 and 1151 to investigate patterns of ecologic changes in space and time during the last 16 million years for the mid-latitude to subarctic North Pacific. High concentrations of radiolarians occurred between 9.0 and 2.7 Ma. Radiolarian species richness was highest in the early middle Miocene at each site and gradually decreased up to about 7 Ma, coinciding with a well-established global cooling trend. A degree of overlap index calculated for radiolarian assemblages revealed 11 faunal change events, of which 8 corresponded to global cooling events and expansions of polar ice sheets. Three of the faunal change events were observed within the peak of radiolarian accumulation rate and were ascribed to changes in primary productivity in the North Pacific rather than global climatic changes. Our assemblage analyses revealed that north-south differentiation in radiolarian assemblages in the northwestern Pacific has existed since 16 Ma and became more distinct via major steps at 6.8 Ma and 2.7 Ma, coinciding with major glaciation events, and that east-west faunal contrasts in the subarctic region became obvious beginning at 11.7 Ma and changed to a different mode around 6.8 Ma. The observed east-west faunal differences possibly reflect east to west climate differences that were characterized by cooler temperatures in the east than the west during the late Miocene (11.7-6.8 Ma) and then by the opposite temperature trend (6.8 Ma-Recent). A severe glaciation at 2.7 Ma played a large role, particularly in temporal changes in radiolarian accumulation rate and assemblage composition.

Daily ice production and polynya area in the Laptev Sea region during 1979-2009

Polynyas in the Laptev Sea are examined with respect to recurrence and interannual wintertime ice production.We use a polynya classification method based on passive microwave satellite data to derive daily polynya area from long-term sea-ice concentrations. This provides insight into the spatial and temporal variability of open-water and thin-ice regions on the Laptev Sea Shelf. Using thermal infrared satellite data to derive an empirical thin-ice distribution within the thickness range from 0 to 20 cm, we calculate daily average surface heat loss and the resulting wintertime ice formation within the Laptev Sea polynyas between 1979 and 2008 using reanalysis data supplied by the National Centers for Environmental Prediction, USA, as atmospheric forcing. Results indicate that previous studies significantly overestimate the contribution of polynyas to the ice production in the Laptev Sea. Average wintertime ice production in polynyas amounts to approximately 55 km3 ± 27% and is mostly determined by the polynya area, wind speed and associated large-scale circulation patterns. No trend in ice production could be detected in the period from 1979/80 to 2007/08.

Dive depth profile and immobilisation data of adult male and female Weddell seals at Drescher Inlet from expedition DRE1998

Adult male and female Weddell seals (Leptonychotes weddellii) were fitted with Time-depth recorders (TDR) at Drescher Inlet (Riiser Larsen Ice Shelf), eastern Weddell Sea coast, in February 1998. Eight of 15 data sets were selected for analyses to investigate the seals' foraging behaviour (doi:10.1594/PANGAEA.511465, doi:10.1594/PANGAEA.511454, doi:10.1594/PANGAEA.511456, doi:10.1594/PANGAEA.511457, doi:10.1594/PANGAEA.511459, doi:10.1594/PANGAEA.511462, doi:10.1594/PANGAEA.511466, doi:10.1594/PANGAEA.511467). These data sets provided simultaneous dive records of eight seals over eight days. The seals primarily foraged within two depth layers, these being from the sea surface to 160 m where temperature and salinity varied considerably, and from 340 to 450 m near the bottom where temperature was lowest and salinity highest, with little variation. While pelagic and benthic diving occurred during daylight, the seals foraged almost exclusively in the upper water column at night. Trawling during daytime confirmed that Pleuragramma antarcticum were by far the most abundant fish both in the pelagial and close to the bottom. Pelagic night-hauls at 110-170 m depth showed highly variable biomass of P. antarcticum with a peak at around midnight. The temporal changes in the local abundance of P. antarcticum, particularly in the pelagial, may explain the trends in the seals' pelagic and benthic foraging activities. This is the first study which describes the jaw movements of a hunting seal which are presumably indicative of feeding events. Trophic links from the Weddell seal to fish, zooplankton and krill, Euphausia superba, are discussed. Another seven data sets did not overlap substantially with the selected time frame (doi:10.1594/PANGAEA.511458, doi:10.1594/PANGAEA.511460, doi:10.1594/PANGAEA.511464, doi:10.1594/PANGAEA.511468, doi:10.1594/PANGAEA.511469, doi:10.1594/PANGAEA.511453, doi:10.1594/PANGAEA.511463). A total of 25 Weddell seals were immobilised during the study period using a combination of ketamine, xylazine, and diazepam. Seven seals were drugged once, 15 seals two times, and three were drugged three times, coming to a total of 46 immobilisation procedures. Narcoses were terminated with yohimbine (doi:10.1594/PANGAEA.438933).

Age model of firn core DML05C98_32 (B32)

In the framework of the European Project for Ice Coring in Antarctica (EPICA), a comprehensive glaciological pre-site survey has been carried out on Amundsenisen, Dronning Maud Land, East Antarctica, in the past decade. Within this survey, four intermediate-depth ice cores and 13 snow pits were analyzed for their ionic composition and interpreted with respect to the spatial and temporal variability of volcanic sulphate deposition. The comparison of the non-sea-salt (nss)-sulphate peaks that are related to the well-known eruptions of Pinatubo and Cerro Hudson in AD 1991 revealed sulphate depositions of comparable size (15.8 ± 3.4 kg/km**2) in 11 snow pits. There is a tendency to higher annual concentrations for smaller snow-accumulation rates. The combination of seasonal sodium and annually resolved nss-sulphate records allowed the establishment of a time-scale derived by annual-layer counting over the last 2000 years and thus a detailed chronology of annual volcanic sulphate deposition. Using a robust outlier detection algorithm, 49 volcanic eruptions were identified between AD 165 and 1997. The dating uncertainty is ±3 years between AD 1997 and 1601, around ±5 years between AD 1601 and 1257, and increasing to ±24 years at AD 165, improving the accuracy of the volcanic chronology during the penultimate millennium considerably.

Mercury content and isotopic composition of teeth, and sex and age of skulls of polar bears collected in Svalbard

We examined the use of mercury (Hg) and nitrogen and carbon stable isotopes in teeth of polar bear (Ursus maritimus) from Svalbard as biotracers of temporal changes in Hg pollution exposure between 1964 and 2003. Teeth were regarded as a good matrix of the Hg exposure, and in total 87 teeth of polar bears were analysed. Dental Hg levels ranged from 0.6 to 72.3 ng/g dry weight and increased with age during the first 10 years of life. A decreasing time trend in Hg concentrations was observed over the recent four decades while no temporal changes were found in the stable isotope ratios of nitrogen (d15N) and carbon (d13C). This suggests that the decrease of Hg concentrations over time was more likely due to a lower environmental Hg exposure in this region rather than a shift in the feeding habits of Svalbard polar bears.

Neogene silicoflaggelates in ODP Leg 104 holes

A quantative study was made of silicoflagellates recovered from Sites 642 (lower Miocene-upper Pliocene), 643 (lower Miocene-upper Miocene), and 644 (upper Pliocene-Quaternary) on the Voring Plateau. Although disconformities are present in these sequences, they represent a much more complete record of the Neogene than was recovered previously in the Norwegian Sea by DSDP Leg 38. Silicoflagellates are rare or absent for glacial sequences younger than 2.65 Ma, and generally sparse and poorly preserved in the lower upper Pliocene and upper Miocene. Lower and middle Miocene assemblages are diverse and generally well preserved. Temporal changes in the silicoflagellate assemblage are indicative of major paleoceanographic changes in the Norwegian Sea. A regional zonation for the Neogene of the Norwegian Sea is proposed, consisting of eleven zones: Naviculopsis lata Zone, N. quadrata Zone (emended), N. ponticula Zone (emended), Distephanus speculum hemisphaericus Zone (new), Caryocha ernestinae Zone (new), Bachmannocena circulus var. apiculata/Caryocha Zone (new), Distephanus crux scutulatus Zone (new), Bachmannocena diodon nodosa Zone (new), Distephanus boliviensis Zone (new), Ds. jimlingii Zone (elevated from subzonal to zonal status) with Subzones a and b (new), and Ds. speculum Zone (new). The ranges and abundances of over 100 species and morphotypes are tabulated.

Simulated Bromoform emission and concentration using the ocean biogeochemistry model MPIOM/HAMOCC forced by 6-hourly NCEP data

Bromoform (CHBr3) is one important precursor of atmospheric reactive bromine species that are involved in ozone depletion in the troposphere and stratosphere. In the open ocean bromoform production is linked to phytoplankton that contains the enzyme bromoperoxidase. Coastal sources of bromoform are higher than open ocean sources. However, open ocean emissions are important because the transfer of tracers into higher altitude in the air, i.e. into the ozone layer, strongly depends on the location of emissions. For example, emissions in the tropics are more rapidly transported into the upper atmosphere than emissions from higher latitudes. Global spatio-temporal features of bromoform emissions are poorly constrained. Here, a global three-dimensional ocean biogeochemistry model (MPIOM-HAMOCC) is used to simulate bromoform cycling in the ocean and emissions into the atmosphere using recently published data of global atmospheric concentrations (Ziska et al., 2013) as upper boundary conditions. Our simulated surface concentrations of CHBr3 match the observations well. Simulated global annual emissions based on monthly mean model output are lower than previous estimates, including the estimate by Ziska et al. (2013), because the gas exchange reverses when less bromoform is produced in non-blooming seasons. This is the case for higher latitudes, i.e. the polar regions and northern North Atlantic. Further model experiments show that future model studies may need to distinguish different bromoform-producing phytoplankton species and reveal that the transport of CHBr3 from the coast considerably alters open ocean bromoform concentrations, in particular in the northern sub-polar and polar regions.

Stable oxygen isotope ratios of marine barite from Cenozoic sediments

We report new data on oxygen isotopes in marine sulfate (delta18O[SO4]), measured in marine barite (BaSO4), over the Cenozoic. The delta18O[SO4] varies by 6x over the Cenozoic, with major peaks 3, 15, 30 and 55 Ma. The delta18O[SO4] does not co-vary with the delta18O[SO4], emphasizing that different processes control the oxygen and sulfur isotopic composition of sulfate. This indicates that temporal changes in the delta18O[SO4] over the Cenozoic must reflect changes in the isotopic fractionation associated with the sulfide reoxidation pathway. This suggests that variations in the aerial extent of different types of organic-rich sediments may have a significant impact on the biogeochemical sulfur cycle and emphasizes that the sulfur cycle is less sensitive to net organic carbon burial than to changes in the conditions of that organic carbon burial. The delta18O[SO4] also does not co-vary with the d18O measured in benthic foraminifera, emphasizing that oxygen isotopes in water and sulfate remain out of equilibrium over the lifetime of sulfate in the ocean. A simple box model was used to explore dynamics of the marine sulfur cycle with respect to both oxygen and sulfur isotopes over the Cenozoic. We interpret variability in the delta18O[SO4] to reflect changes in the aerial distribution of conditions within organic-rich sediments, from periods with more localized, organic-rich sediments, to periods with more diffuse organic carbon burial. While these changes may not impact the net organic carbon burial, they will greatly affect the way that sulfur is processed within organic-rich sediments, impacting the sulfide reoxidation pathway and thus the delta18O[SO4]. Our qualitative interpretation of the record suggests that sulfate concentrations were probably lower earlier in the Cenozoic.

d15N of trap WR2

Temporal changes in d15N values of sinking particles collected with sediment traps in the Benguela upwelling regime off southwest Africa mirrored variations in the input of inorganic nitrogen to the surface water. Reductions in d15N (to as low as 2.5 per mil) corresponded to low sea surface temperatures during austral spring and late austral autumn/early winter, indicating increased nitrate availability due to the presence of recently upwelled water. High particulate fluxes accompanied the low d15N values and sea surface temperatures, reflecting increased productivity, fueled by the upwelled nutrients. High d15N values (up to 13.1 per mil) coincided with high sea surface temperatures and low particle fluxes. In this area, the seaward extension of upwelling filaments, which usually occurs twice yearly, brings nutrient-rich water to the euphotic zone and leads to elevated productivity and relatively lower d15N values of the particulate nitrogen. Satellite images of ocean chlorophyll show that productivity variations coincide with d15N changes. The observed isotopic pattern does not appear to have been caused by variations in the species composition of the phytoplankton assemblage. Calculations based on d15N of the sinking particulate nitrogen show that the surface nitrate pool was more depleted during late austral summer/early fall and mid-winter and that supply exceeded demand during the intense spring bloom and in late austral fall. The main uncertainty associated with these estimates is the effect of diagenesis on d15N and possible variability in preservation of the isotope signal between periods of high and low particle flux.

PEECE II mesocosm experiment: Dynamics of extracellular enzyme activities in seawater under changed atmospheric pCO2, 2011

As part of the PeECE II mesocosm project, we investigated the effects of pCO2 levels on the initial step of heterotrophic carbon cycling in the surface ocean. The activities of microbial extracellular enzymes hydrolyzing 4 polysaccharides were measured during the development of a natural phytoplankton bloom under pCO2 conditions representing glacial (190 µatm) and future (750 µatm) atmospheric pCO2. We observed that (1) chondroitin hydrolysis was variable throughout the pre-, early- and late-bloom phases, (2) fucoidanase activity was measurable only in the glacial mesocosm as the bloom developed, (3) laminarinase activity was low and constant, and (4) xylanase activity declined as the bloom progressed. Concurrent measurements of microbial community composition, using denaturing-gradient gel electrophoresis (DGGE), showed that the 2 mesocosms diverged temporally, and from one another, especially in the late-bloom phase. Enzyme activities correlated with bloom phase and pCO2, suggesting functional as well as compositional changes in microbial communities in the different pCO2 environments. These changes, however, may be a response to temporal changes in the development of phytoplankton communities that differed with the pCO2 environment. We hypothesize that the phytoplankton communities produced dissolved organic carbon (DOC) differing in composition, a hypothesis supported by changing amino acid composition of the DOC, and that enzyme activities responded to changes in substrates. Enzyme activities observed under different pCO2 conditions likely reflect both genetic and population-level responses to changes occurring among multiple components of the microbial loop.

Analyses of ferromanganese micronodules from the central Arctic Ocean

In order to determine geochemical compositions of Late Cenozoic Arctic seawater, oxide fractions were chemically separated from 15 samples of hand-picked ferromanganese micronodules (50-300 mu m). The success of the chemical separation is indicated by the fact that >97% of the Sr in the oxide fraction is seawater-derived. Rare-earth element (REE) abundances of the Arctic micronodule oxide fractions are much lower than those of bulk Fe-Mn nodules from other ocean basins of the world (e.g., 33 vs. 145 ppm Nd), but the Arctic oxides are enriched in Ce relative to Nd (Ce-N/Nd-N=2.2+/-0.5) and have convex-upward, shale-normalized REE patterns (Nd-N/Gd-N=0.61+/-0.06, Gd-N/Yb-N = 1.5+/-0.2, Nd-N/Yb-N = 0.9+/-0.2), typical of other hydrogenous and diagenetic marine Fe-Mn-oxides. Bulk sediment samples from the central Arctic Ocean have REE abundances and patterns that are characteristic of those of post-Archean shale. Non-detrital fractions (calcite + oxide coatings) of Recent Arctic foraminifera have REE abundances and patterns similar to those of Recent foraminifera from the Atlantic Ocean. Electron microprobe analyses (n=178) of transition elements in 29 Arctic Fe-Mn micronodules from five different stratigraphic intervals of Late Cenozoic sediment indicate that oxide accretion occurred as a result of hydrogenetic and diagenetic processes close to the sediment-seawater interface. Transition element ratios suggest that no oxide accretion occurred during transitions from oxic to suboxic diagenetic conditions. Only K is correlated with Si and Al, and ratios of these elements suggest that they are associated with illite or phillipsite. Ca and Mg are correlated with Mn, which indicates variable substitution of these elements from seawater into the manganate phase. The geochemical characteristics of Arctic Fe-Mn micronodules indicate that the REEs of the oxide fractions were ultimately derived from seawater. However, because of minute contributions of Sr from siliciclastic detritus during diagenesis or during the chemical leaching procedure, Sr isotope compositions of the oxide fractions cannot be used to trace temporal changes in the Sr-87/Sr-86 ratio of Arctic seawater or to improve the chronostratigraphy.

Chemical and isotope compositions of sediments from DSDP Hole 86-576A and Core LL44-GPC-3

A record of changes in Pb and Sr isotopic composition of two cores (DSDP 86-576A and LL44- GPC-3) from the red clay region of the central North Pacific has been determined for the past 60-65 million years. The isotope records of the eolian silicate fraction of the red clays reflect the change in source area as the core sites migrated under different wind systems. The Sr isotope compositions of eolian silicate material are consistent with Asian loess and North American arc volcanism that has been recognized from mineralogical studies. The silicate-bound eolian Pb isotopic compositions similarly reflect Asian loess and arc volcanism. The isotope records of three ferromanganese crusts from similar locations in the central Pacific are similar to the eolian component of red clays, but offset to less radiogenic values. This may be due to two mechanisms: (1) Pb that can be removed from eolian material by seawater is much less radiogenic, or less likely (2) hydrothermal Pb can be transported further away from venting sites through particle exchange with seawater, despite hydrothermal venting acting as a net sink of oceanic Pb. The temporal changes in Pb isotopes in the ferromanganese crusts, bulk red clays and eolian silicates are similar although offset from each other suggesting that eolian deposition is an important source of Pb to seawater and to ferromanganese crusts. This contrasts with the Atlantic and Southern Ocean where more intense deep water flow leads to isotopic gradients in FeMn crusts that do not reflect surface water conditions immediately above the crust. A mechanism is proposed which accounts for Pacific deepwater Pb being isotopically influenced by eolian deposition.