Geochemistry of subducted volcaniclastic sediments from Mariana arc magmas

The phase relations of natural volcaniclastic sediments from the west Pacific Ocean were investigated experimentally at conditions of 3-6 GPa and 800-900 °C with 10 wt.% added H2O (in addition to ~ 10 wt.% structurally-bound H2O) to induce hydrous melting. Volcaniclastic sediments are shown to produce a sub-solidus assemblage of garnet, clinopyroxene, biotite, quartz/coesite and the accessory phases rutile ± Fe-Ti oxide ± apatite ± monazite ± zircon. Hydrous melt appears at temperatures exceeding 800-850 °C, irrespective of pressure. The melt-producing reaction consumes clinopyroxene, biotite and quartz/coesite and produces orthopyroxene. These phase relations differ from those of pelagic clays and K-bearing mid ocean ridge basalts (e.g. altered oceanic crust) that contain phengite, rather than biotite, as a sub-solidus phase. Despite their relatively high melt productivity, the wet solidus for volcaniclastic sediments is found to be higher (825-850 °C) than other marine sediments (700-750 °C) at 3 GPa. This trend is reversed at high-pressure conditions (6 GPa) where the biotite melting reaction occurs at lower temperatures (800-850 °C) than the phengite melting reaction (900-1000 °C). Trace element data was obtained from the 3 GPa run products, showing that partial melts are depleted in heavy rare earth elements (REE) and high field strength elements (HFSE), due to the presence of residual garnet and rutile, and are enriched in large ion lithophile elements (LILE), except for Sr and Ba. This is in contrast to previous experimental studies on pelagic sediments at sub-arc depths, where Sr and Ba are among the most enriched trace elements in glasses. This behavior can be partly attributed to the presence of residual apatite, which also host some light REE in our supra-solidus residues. Our new experimental results account for a wide range of trace element and U-series geochemical features of the sedimentary component of the Mariana arc magmas, including imparting a substantial Nb anomaly to melts from an anomaly-free protolith.

Constructing a stacked benthic d18O record

Composite stacks were constructed by superimposing 6 to 13 benthic foraminiferal d18O records covering the period 0-850 ka. An initial timescale for each core was established using radioisotopic age control points and assuming constant sedimentation rates between these points. The average of these records is our 13-core "untuned" stack. Next, we matched the 41 kyr component of each record individually to variations in Earth's obliquity. Four of the 13 records produced timescales that were inconsistent with one or more of the known radioisotopic ages. The nine remaining cores were averaged to create a "minimally tuned" stack. Six of the minimally tuned cores were assembled into a "tropical" stack. For each stack we estimated the uncertainty envelope from the standard deviation of the constituents. Spectral analysis of the three stacks indicates that benthic d18O is dominated by a 100 kyr oscillation that has a narrow spectral peak. The contribution of precession to the total variance is small when compared to prior results from planktic stacks.

Response of nannoplankton to major changes in sea-surface temperature at the South Chatham Rise, southeastern New Zealand

A high-resolution history of paleoceanographic changes in the subpolar waters of the southern margin of the Subtropical Convergence Zone during the last 130 kyr, is present in foraminiferal assemblages of DSDP Site 594. The foraminifera indicate that sea-surface temperatures during the Last Interglacial Climax were warmer than today, and that between substage 5d through to the end of isotope stage 2, temperatures were mostly cooler than Holocene temperatures. The paleotemperatures suggest that (1) the Subtropical Convergence was located over the site during substage 5e, later moving further north, then moving southwards to near the site during the Holocene, and (2) the Polar Front was positioned over the Site during glacial stages 6, 4, 2 and possibly parts of stage 3. Several major events are indicated by the nannofloral assemblages during these large changes in sea-surface temperature and associated reorganization of ocean circulation. First, the time-progressive trends between E. huxleyi and medium to large Gephyrocupsa are unique to this site, with E. huxleyi dominating over medium Gephyrocupsa during stages 5c-a, middle part of stage 4 and after the middle point of stage 3. This unusual trend may (at least partly) be caused by the shift of the Polar Front across the site. Second, upwelling flora (E. huxleyi and small placoliths) increase in abundance during stages 1, 3 and 5, suggesting that upwelling or disturbance of water stratification took place during the interglacials. Thirdly, there are no significant differences between the distribution patterns of the various morphotypes of medium to large Gephyrocupsu, and the combined value of all medium Gephyrocupsu increases in abundance during glacials (stages 2 and 4 and the end of stage 6), similar to the abundance trends in benthic foraminifera. Finally, subordinate nannofossil taxa also show distinctive climatic trends during the last glacial cycle: (1) Syrucosphaera spp. are present in increased abundance during warmer extremes in climate (substages 5e, 5a, and stage 1); (2) Coccolithus pelagicus and Culcidiscus leptoporus dominate the subordinate nannofossil taxa, and their relative proportions seem to provide a useful paleoceanographic index, with C. pelagicus dominating when the Polar Front Zone is over the site (stages 6, 4 and 2), whilst C. leptoporus is relatively more abundant when the STC is positioned over the site (stages 1 and 5e). Increased abundance of C. pelagicus also can indicate intensified coastal upwelling.

Dissolved and dissolvable iron concentrations and ligand characteristics in samples taken during POLARSTERN expedition ARK-XXII/2 to the Arctic Ocean

The speciation of iron was investigated in three shelf seas and three deep basins of the Arctic Ocean in 2007. The dissolved fraction (<0.2 µm) and a fraction < 1000 kDa were considered here. In addition, unfiltered samples were analyzed. Between 74 and 83% of dissolved iron was present in the fraction < 1000 kDa at all stations and depth, except at the chlorophyll maximum (42-64%). Distinct trends in iron concentrations and ligand characteristics were observed from the shelf seas toward the central deep basins, with a decrease of total dissolvable iron ([TDFe] > 3 nM on the shelves and [TDFe] < 2 nM in the Makarov Basin). A relative enrichment of particulate Fe toward the bottom was revealed at all stations, indicating Fe export toward the deep ocean. In deep waters, dissolved ligands became less saturated with Fe (increase of [Excess L]/[Fe]) from the Nansen Basin via the Amundsen Basin toward the Makarov Basin. This trend was explained by the reactivity of the ligands, higher (log alpha > 13.5) in the Nansen and Amundsen basins than in the Makarov Basin (log alpha <13) where the sources of Fe and ligands were limited. The ligands became nearly saturated with depth in the Amundsen and Nansen Basins, favoring Fe removal in the deep ocean, whereas in the deep Makarov Basin, they became unsaturated with depth. Still here scavenging occurred. Although scavenging of Fe was attenuated by the presence of unsaturated organic ligands, their low reactivity in combination with a lack of sources of Fe in the Makarov Basin might be the reason of a net export of Fe to the sediment.

Pigment, carbohydrate and protein content of microbial mats from northern Victoria Land lake sediments

The composition of algal pigments and extracellular polymeric substances (EPS) was determined in microbial mats from two lakes in Victoria Land (Continental Antarctica) with different lithology and environmental features. The aim was to expand knowledge of benthic autotrophic communities in Antarctic lacustrine ecosystems, providing reference data for future assessment of possible changes in environmental conditions and freshwater communities. The results of chemical analyses were supported by microscopy observations. Pigment profiles showed that filamentous cyanobacteria are dominant in both lakes. Samples from the water body at Edmonson Point had greater biodiversity, fewer pigments and lower EPS ratios than those from the lake at Kar Plateau. Differences in mat composition and in pigment and EPS profile between the two lakes are discussed in terms of local environmental conditions such as lithology, ice-cover and UV radiation. The present study suggests that a chemical approach could be useful in the study of benthic communities in Antarctic lakes and their variations in space and time.

CaCO3 content, terrigenous components, foraminifera abundance and age of sediment core MD95-2006, Barra Fan, UK

Lithology, lithic petrology, planktonic foraminiferal abundances, and clastic grain sizes have been determined in a 30 m-long core recovered from the Barra Fan off northwest Scotland. The record extends back to around 45 kyr B.P., with sedimentation rates ranging between 50 and 200 cm/kyr. The abundance of ice-rafted debris indicates 16 glacimarine events, including temporal equivalents to Heinrich events 1-4. Enhanced concentrations of basaltic material derived from the British Tertiary Province suggest that the glacimarine sediments record variations in a glacial source on the Hebrides shelf margin. Glacimarine zones are separated by silty intervals with high planktonic foraminifera concentrations that reflect an interstadial circulation regime in the Rockall Trough. The results suggest that the last British Ice Sheet fluctuated with a periodicity of 2000-3000 years, in common with the Dansgaard-Oeschger climate cycle.

Planktonic foraminiferal and stable oxygen isotope record of Holocene sediments from the Norwegian Sea

High-resolution records from IMAGES core MD95-2011 in the eastern Norwegian Sea provide evidence for relatively large- and small-scale high-latitude climate variability throughout the Holocene. During the early and mid-Holocene a situation possibly driven by consistent stronger westerlies increased the eastward influence of Arctic intermediate and near-surface waters. For the late Holocene a relaxation of the atmospheric forcing resulted in increased influence of Atlantic water. The main changes in Holocene climate show no obvious connection to changing solar irradiance, and spectral analysis reveals no consistent signature for any periodic behavior of Holocene climate at millennial or centennial timescales. There are, however, indications of consistent multidecadal variability.

IODP Expedition 337, Shimokita Deep Coalbed Biosphere

Microbial life inhabits deeply buried marine sediments, but the extent of this vast ecosystem remains poorly constrained. Here we provide evidence for the existence of microbial communities in ~40° to 60°C sediment associated with lignite coal beds at ~1.5 to 2.5 km below the seafloor in the Pacific Ocean off Japan. Microbial methanogenesis was indicated by the isotopic compositions of methane and carbon dioxide, biomarkers, cultivation data, and gas compositions. Concentrations of indigenous microbial cells below 1.5 km ranged from <10 to ~10**4 cells cm**-3. Peak concentrations occurred in lignite layers, where communities differed markedly from shallower subseafloor communities and instead resembled organotrophic communities in forest soils. This suggests that terrigenous sediments retain indigenous community members tens of millions of years after burial in the seabed.

Biometrics, fatty acid composition and stable isotopic ratios of five seabird species from Kongsfjorden, Svalbard

Marine birds are important predators in the marine ecosystem, and dietary studies can give useful information about their feeding ecology, food webs and oceanographic variability. The aim of this study was to increase our understanding of the diet and trophic level of the seabirds breeding in Kongsfjorden, Svalbard. We have used fatty acids and stable isotopes, both of which integrate diet information over space and time, to determine trophic relationships in marine food webs. Fatty acid compositions of muscle from Little auk (Alle alle), Brünnich's guillemot (Uria lomvia), Black-legged kittiwake (Rissa tridactyla), Northern fulmar (Fulmarus glacialis) and Glaucous gull (Larus hyperboreus) were determined and compared with their prey species. Canonical analysis (CA) showed that fatty acid composition differed among the five seabird species. Little auk, Black-legged kittiwake and Northern fulmar had high levels of the Calanus markers 20:1n9 and 22:1, indicating that these seabirds are a part of the Calanus food chain. Brünnich's guillemot differed from the other species with much lower levels of 20:1n9 and 22:1. Brünnich's guillemot is a pursuit diver feeding on fish and amphipods deeper in the water column, below 30 m. Glaucous gull also differed from the other seabird species, with a larger variation in the fatty acid composition indicating a more diverse diet. Trophic level analysis placed Little auk at the lowest trophic level, Brünnich's guillemot and Black-legged kittiwake at intermediate levels and Glaucous gull and Northern fulmar at the highest trophic level.

Concentrations of persistant organic pollutants in Great skua eggs (Stercorarius skua) from Shetland 1980 and 2008

Concentrations of POPs in Great skua eggs from Shetland are among the highest in North Atlantic seabirds, with up to 11,600 µg/kg (ww) DDE and up to 17,900 µg/kg ww SumPCB. Concentrations of legacy POPs were significantly lower in 2008 than 1980. Decreases were greatest for least persistent compounds. Median SumPBDEs increased from 99 µg/kg ww in 1980 to 173 µg/kg ww in 2008. There were changes in Great skua breeding season diet, with more adult Herring and Mackerel and less Sandeel. These changes increase exposure to POPs, since Herring and Mackerel accumulate more POPs than Sandeels. In both years, eggs with higher d15N had higher POP concentrations. In 1980, birds feeding more on demersal discard fish from trawl fisheries and less on Sandeels, had higher POP levels in eggs. In 2008, individuals feeding more on Herring and Mackerel, and less on discards, had higher POP levels in eggs.

Relative abundances of foraminifera and radiocarbon ages of selected cores obtained from the Nordic and Barents Sea

Ocean circulation changes along the continental shelf of the Nordic and Barents Seas have been investigated in order to reconstruct regional changes in the inflow of Atlantic Water (AW) through the last 16,000 calibrated (cal) years (yr) B.P. We have selected five time-slices representing the late glacial (16,000-15,000 cal yr B.P.), the Bølling-Allerød warm interstadials (14,500-13,500 cal yr B.P.), the Younger Dryas cold stadial (12,500-11,500 cal yr B.P.), the early Holocene (9500-7500 cal yr B.P.) and the late Holocene (4000-2000 cal yr B.P.). Twelve previously published records of the distribution of benthic foraminifera faunas and ice-rafted debris have been compiled. The earliest sign of Atlantic Water inflow was recorded at the northern Iceland shelf at 16,000-15,000 cal yr B.P. The inflow of warm AW to the Nordic Seas shelf has been persistent since, but with variable strength and geographic pattern. An apparent zonal seesaw pattern in the strength of the Norwegian Atlantic Current (NwAC) and the Irminger Current (IC) during the late glacial, Bølling-Allerød and Younger Dryas periods was found. During the Holocene, no zonal differences in the inflows of NwAC and IC were found. A strong meridional gradient with warmer conditions at lower latitudes and relatively cold conditions at high northern latitudes existed.

Chlorophyll a concentration, and proportion of time in the water column obtained by instrumented bowhead whales

Sixty hours of direct measurements of fluorescence were collected from six bowhead whales (Balaena mysticetus) instrumented with fluorometers in Greenland in April 2005 and 2006. The data were used to (1) characterize the three-dimensional spatial pattern of chlorophyll-a (Chl-a) in the water column, (2) to examine the relationships between whale foraging areas and productive zones, and (3) to examine the correlation between whale-derived in situ values of Chl-a and those from concurrent satellite images using the NASA MODIS (Moderate Resolution Imaging Spectroradiometer) EOS-AQUA satellite (MOD21, SeaWifs analogue OC3M and SST MOD37). Bowhead whales traversed 1600 km**2, providing information on diving, Chl-a structure and temperature profiles to depths below 200 m. Feeding dives frequently passed through surface waters ( >50 m) and targeted depths close to the bottom, and whales did not always target patches of high concentrations of Chl-a in the upper 50 m. Five satellite images were available within the periods whales carried fluorometers. Whales traversed 91 pixels collecting on average 761 s (SD 826) of Chl-a samples per pixel (0-136 m). The depth of the Chl-a maximum ranged widely, from 1 to 66 m. Estimates of Chl-a made from the water-leaving radiance measurements using the OC3M algorithm were highly skewed with most samples estimated as <1 mg/m**3 Chl-a, while data collected from whales had a broad distribution with Chl-a reaching >9 mg/m**3. The correlation between the satellite-derived and whale-derived Chl-a maxima was poor, a linear fit explained only 10% of the variance.

Petrology, mineralogy, and chemistry of basaltic rocks at DSDP Leg 81 Holes

We detail the petrography and mineralogy of 145 basaltic rocks from the top, middle, and base of flow units identified on shipboard along with associated pyroclastic samples. Our account includes representative electron microprobe analyses of primary and secondary minerals; 28 whole-rock major-oxide analyses; 135 whole-rock analyses each for 21 trace elements; 7 whole-rock rare-earth analyses; and 77 whole-rock X-ray-diffraction analyses. These data show generally similar petrography, mineralogy, and chemistry for the basalts from all four sites; they are typically subalkaline and consanguineous with limited evolution along the tholeiite trend. Limited fractionation is indicated by immobile trace elements; some xenocrystic incorporation from more basic material also occurred. Secondary alteration products indicate early subaerial weathering followed by prolonged interaction with seawater, most likely below 150°C at Holes 552, 553A, and 554A. At Hole 555, greenschist alteration affected the deepest rocks (olivine-dolerite) penetrated, at 250-300°C.

Geochemistry of Miocene "blue tuff" samples

Distinctive, massive to stratified, pale blue volcaniclastics, initially referred to as the "blue tuff," were encountered at all four sites drilled during ODP Leg 127 in the Japan Sea. Detailed vertical sequence analysis, plagioclase chemistry, plagioclase 87Sr/86Sr isotopic composition, and 40Ar/39Ar age dating indicate that thick sequences of the blue tuff are not genetically related. Blue tuffs at Hole 794B were apparently deposited by density flows at ambient temperature. Deposition was penecontemporaneous with a large submarine phreatomagmatic eruption at 14.9 Ma in bathyal or deeper water depths. The blue tuffs at this location comprise mostly reworked hydroclastic glass shards and lesser amounts of plagioclase crystals. Pyrogenic plagioclase has an average An mole% of 18±3. Comparison of blue tuff plagioclase compositions with the composition of plagioclase from acoustic basement at Site 794 suggests that these rocks are not genetically related. As such, the extrapolation of sediment accumulation rate data in conjunction with this more precise age for the blue tuff corroborates previous minimum age estimates of 16.2 Ma for acoustic basement at Site 794. Blue tuffs at Hole 796B were probably deposited at ambient temperatures by downslope slumping and density flow of reworked pyrogenic debris. This debris includes abundant bubble wall glass shards and plagioclase crystals, with variable admixture of volcanic lithic and intrabasinal fragments. Pyrogenic fragments were produced by subaerial or shallow submarine, magmatic eruptions dated at 7.6 Ma. Blue tuffs contain a heterogeneous mixture of unrelated fragments including a mixed population of plagioclase crystals. The average An mole% of the predominant, probable comagmatic, plagioclase population is 30±4. The two sequences of blue tuff studied are distinct in age, mineral composition, and the eruptive origin of pyroclastic fragments. Preliminary 87Sr/86Sr isotopic compositions of plagioclase, however, indicates that blue tuffs at both locations are the product of typical, subduction-related island arc magmatism. Based on the results of this study, there is no justification for stratigraphic correlation of widespread, Miocene, blue to blue-gray bentonitic tuff and tuffaceous sandstones nor the interpretation that these strata are indicative of regional, explosive submarine volcanism genetically related to rifting and formation of the Japan Sea. Rather, these reworked pyroclastic strata of intermediate composition were deposited over a protracted 6-8 m.y. period in association with widespread, subduction-related submarine to subaerial volcanism in the Japan Sea backarc basin.

Oxygen isotope and Mg/Ca record of planktonic foraminifera of sediment core MD01-2390

Changes in the local freshwater budget over the last 22,000 years have been estimated from a sediment core located in the southern South China Sea (SCS) using a combined approach of Mg/Ca and oxygen isotopes on the planktonic foraminifera Globigerinoides ruber (white) sensu stricto (s.s.). Core MD01-2390 (06°28,12N, 113°24,56E; water depth 1591 m) is located near the glacial paleo-river mouths of the Baram, Rajang and North Sunda/Molengraaff Rivers that drained the exposed Sunda Shelf. The delta18Oseawater record reveals lower average values (-0.96±0.18 per mil) during the Last Glacial Maximum (LGM) when compared with modern values (-0.54±0.18 per mil). Low salinity during the LGM is interpreted to reflect a higher freshwater contribution due to a greater proximity of the core site to the mouths of the Baram, Rajang and North Sunda/Molengraaff Rivers at that time. A general deglacial increasing trend in salinity due to the progressive landward displacement of the coastline during deglacial shelf flooding is punctuated by several short-term shifts towards higher and lower salinity that are likely related to abrupt changes in the intensity of the East Asian summer monsoon. Thus, the deglacial delta18Oseawater changes reflect the combined effects of sea-level-induced environmental changes on the shelf (e.g. phases of retreat and breakdown of the shelf drainage systems) and East Asian monsoon climate change. Lower salinity than at present during the Early Holocene may be attributed to an increase in summer monsoonal precipitation that is corroborated by previous marine and terrestrial studies that report a Preboreal-Early Holocene monsoon optimum in the Asian monsoon region.