Os isotope ratios of Late Eocene sediments from the tropical Pacific

High resolution records (ca. 100 kyr) of Os isotope composition (187Os/188Os) in bulk sediments from two tropical Pacific sites (ODP Sites 1218 and 1219) capture the complete Late Eocene 187Os/188Os excursion and confirm that the Late Eocene 187Os/ 188Os minimum, earlier reported by Ravizza and Peucker-Ehrenbrink (2003, doi:10.1016/S0012-821X(03)00137-7), is a global feature. Using the astronomically tuned age models available for these sites, it is suggested that the Late Eocene 187Os/188Os minimum can be placed at 34.5 +/- 0.1 Ma in the marine records. In addition, two other distinct features of the 187Os/188Os excursion that are correlatable among sections are proposed as chemostratigraphic markers which can serve as age control points with a precision of ca. +/-0.1 Myr. We propose a speculative hypothesis that higher cosmic dust flux in the Late Eocene may have contributed to global cooling and Early Oligocene glaciation (Oi-1) by supplying bio-essential trace elements to the oceans and thereby resulting in higher ocean productivity, enhanced burial of organic carbon and draw down of atmospheric CO2. To determine if the hypothesis that enhanced cosmic dust flux in the Late Eocene was a cause for the 187Os/188Os excursion can be tested by using the paired bulk sediment and leachate Os isotope composition; 187Os/188Os were also measured in sediment leachates. Results of analyses of leachates are inconsistent between the south Atlantic and the Pacific sites, and therefore do not yield a robust test of this hypothesis. Comparison of 187Os/188Os records with high resolution benthic foraminiferal delta18O records across the Eocene-Oligocene transition suggests that 187Os flux to the oceans decreased during cooling and ice growth leading to the Oi-1 glaciation, whereas subsequent decay of ice-sheets and deglacial weathering drove seawater 187Os/188Os to higher values. Although the precise timing and magnitude of these changes in weathering fluxes and their effects on the marine 187Os/188Os records are obscured by recovery from the Late Eocene 187Os/188Os excursion, evidence of the global influence of glaciation on supply of Os to the ocean is robust as it has now been documented in both Pacific and Atlantic records.

Geochemistry of ash layers from the Bonin Forearc

Many ash-rich layers, varying from a few millimeters to several centimeters thick, were identified in the sedimentary sequences penetrated during Ocean Drilling Program Leg 125 at Sites 782, 784, and 786, located about 400 to 500 km south of Tokyo in the Bonin forearc. The total age range of the ash layers is from Eocene to Pleistocene, although not all sites cover this full span. The ashes consist of vitric, microlite-bearing, and crystal-rich components; the glassy shards are typically highly vesicular, with elongate, flattened bubbles. The dominant crystalline phases are orthopyroxene, clinopyroxene, and plagioclase. The major-element compositions of individual vitric shards collected from selected layers of Holes 782A, 784A, and 786A were determined by electron microprobe analyses; particular care was taken to ensure that the analytical results were not compromised by electron beam damage to the glasses. Compositions range from basalt through andesite and dacite to rhyolite and generally belong to a tholeiitic, low-K suite. There is no indication of any regular secular change during the evolution of the Bonin arc from tholeiitic through calc-alkalic to alkali compositions with time. In Holes 782A and 784A, some high-K rhyolite compositions of late Miocene and Pleistocene age are present. A clear chemical distinction has existed since arc inception between the source(s) of these ashes and the upper mantle source(s) tapped during construction of the igneous basement that formed the forearc.

Iron and carbon geochemistry of sediment core GeoB1401-4

Iron speciation was determined in hemiplegic sediments from a high productivity area to investigate systematically the early diagenetic reactivity of Fe. A combination of various leaching agents (1 M HCI, dithionite buffered in citrate/acetic acid, HF/H2SO4, acetic Cr(II)) was applied to sediment and extracted more than 80% of total Fe. Subsequent Fe species determination defined specific mineral fractions that are available for Fe reduction and fractions formed as products of Fe diagenesis. To determine the Fe speciation of (sheet) silicates we explored an extraction procedure (HF/H2SO4) and verified the procedure by application to standard rocks. Variations of Fe speciation of (sheet) silicates reflect the possible formation of Fe-bearing silicates in near surface sediments. The same fraction indicates a change in the primary input at greater depth, which is supported by other parameters. The Fe(II)/ Fe(III) -ratio of total sediment determined by extractions was compared with Mössbauer-spectroscopy ] at room temperature and showed agreement within 10%. M6ssbauer-spectroscopy indicates the occurrence of siderite in the presence of free sulfide and pyrite, supporting the importance of microenvironments during mineral formation. The occurrence of other Fe(II) bearing minerals such as ankerite (Ca-, Fe-, Mg-carbonate) can be presumed but remains speculative.

(Table 1) Lead, thorium and uranium isotopic concentration and ages of zircons from Yenisey Ridge metapelites

Reconstruction of the geologic history of the Yenisey Ridge, which developed as an accretionary collision orogen on the western margin of the Siberian craton is essential to understanding the evolution of mobile belts surrounding older cratons, as well as to resolving the recently much debated problem of whether Siberia was part of the supercontinent Rodinia. Available paleotectonic models suggest that this supercontinent was assembled at the Middle-Late Riphean boundary (1100-900 Ma) as a result of the Grenville orogeny, the first long-lived mountain building event which occurred in geosynclinal areas during the Neogaea. However, the character of crustal evolution at that stage is still speculative due to the lack of reliable and conclusive isotope data. In many current geodynamic models, a common underlying assumption is that the Yenisey Ridge showed very little endogenic activity for 1 Gyr, from the time of Tarak granite emplacement (1900-1840 Ma) to the Middle Neoproterozoic (~750 Ma). On the basis of this assumption, several recent studies suggested the absence of Grenvillian collisional events within the Yenisey Ridge. The results of the SHRIMP II U-Pb analysis of rift-related plagiogranites of the Nemtikha Complex, Yenisey Ridge (1380-1360 Ma) suggest an increase in magmatic activity in the Mesoproterozoic. Interpretation of these results in terms of a supercontinent cycle may help find evidence for possible occurrence of the Grenville orogeny on the western margin of the Siberian craton. With this in mind, we attempted to reconstruct using recent geochronological constraints the evolution of metapelitic rocks from the Teya polymetamorphic complex (TPMC), which is a good example of superimposed zoning of low and medium-pressure facies series. High precision age determinations from rock complexes formed in different geodynamic settings under different thermodynamic conditions and geothermal gradients were used to distinguish several major metamorphic events and unravel their time relations with tectonic and magmatic activity in the region.

Biogeochemical characterization of pennate diatom and Melosira arctica ice algal aggregates in the Central Arctic Ocean collected in summer 2011 and 2012

Sea-ice diatoms are known to accumulate in large aggregates in and under the sea ice including melt ponds. In the Arctic, they can contribute substantially to particle export when sinking from the ice. The role and regulation of microbial aggregation in the highly seasonal, nutrient- and light-limited Arctic sea-ice ecosystem is not yet well understood, and may vary in relation to the fate of the Arctic sea-ice cover. To elucidate the mechanism controlling the formation and export of algal aggregates from sea ice, we investigated samples taken in late summer 2011 and 2012, during two cruises to the Eurasian Basin of the Central Arctic Ocean. Dense, spherical aggregates composed mainly of pennate diatoms, and filamentous aggregates formed by Melosira arctica were found in different degradation stages, with carbon to Chlorophyll a ratios ranging from 110 to 66700, and carbon to nitrogen molar ratios of 8-35 and 9-40, respectively. Fresh sub-ice algal aggregate densities ranged between 1 and 17 aggregates/m**2, corresponding to a net primary production of 0.4-40 mg C/m**2/d, contributing 3-80% of total biomass and up to 94% of total production at a local scale. A key factor controlling buoyancy of the aggregates was light intensity, regulating photosynthetic oxygen production and flotation by gas bubbles trapped within the mucous matrix, even at low ambient nutrient concentrations. Our data was used to evaluate the factors regulating the distribution and importance of the Arctic algal aggregates as carbon source for pelagic and benthic communities.

Mesocosm experiment Cape Verde 2012: Data

Two 7-day mesocosm experiments were conducted in October 2012 at the Instituto Nacional de Desenvolvimento das Pescas (INDP), Mindelo, Cape Verde. Surface water was collected at night before the start of the respective experiment with RV Islândia south of São Vicente (16°44.4'N, 25°09.4'W) and transported to shore using four 600L food safe intermediate bulk containers. Sixteen mesocosm bags were distributed in four flow-through water baths and shaded with blue, transparent lids to approximately 20% of surface irradiation. Mesocosm bags were filled from the containers by gravity, using a submerged hose to minimize bubbles. The accurate volume inside the individual bags was calculated after addition of 1.5 mmol silicate and measuring the resulting silicate concentration. The volume ranged from 105.5 to 145 L. The experimental manipulation comprised addition of different amounts of inorganic N and P. In the first experiment, the P supply was changed at constant N supply in thirteen of the sixteen units, while in the second experiment the N supply was changed at constant P supply in twelve of the sixteen units. In addition to this, "cornerpoints" were chosen that were repeated during both experiments. Four cornerpoints should have been repeated, but setting the nutrient levels in one mesocosm was not succesfull and therefore this mesocosm also was set at the center point conditions. Experimental treatments were evenly distributed between the four water baths. Initial sampling of the mesocosms on day 1 of each run was conducted between 9:45 and 11:30. After nutrient manipulation, sampling was conducted on a daily basis between 09:00 and 10:30 for days 2 to 8.

Mesocosm experiment Cape Verde 2012: Setup

Two 7-day mesocosm experiments were conducted in October 2012 at the Instituto Nacional de Desenvolvimento das Pescas (INDP), Mindelo, Cape Verde. Surface water was collected at night before the start of the respective experiment with RV Islândia south of São Vicente (16°44.4'N, 25°09.4'W) and transported to shore using four 600L food safe intermediate bulk containers. Sixteen mesocosm bags were distributed in four flow-through water baths and shaded with blue, transparent lids to approximately 20% of surface irradiation. Mesocosm bags were filled from the containers by gravity, using a submerged hose to minimize bubbles. The accurate volume inside the individual bags was calculated after addition of 1.5 mmol silicate and measuring the resulting silicate concentration. The volume ranged from 105.5 to 145 L. The experimental manipulation comprised addition of different amounts of inorganic N and P. In the first experiment, the P supply was changed at constant N supply in thirteen of the sixteen units, while in the second experiment the N supply was changed at constant P supply in twelve of the sixteen units. In addition to this, "cornerpoints" were chosen that were repeated during both experiments. Four cornerpoints should have been repeated, but setting the nutrient levels in one mesocosm was not succesfull and therefore this mesocosm also was set at the center point conditions. Experimental treatments were evenly distributed between the four water baths. Initial sampling of the mesocosms on day 1 of each run was conducted between 9:45 and 11:30. After nutrient manipulation, sampling was conducted on a daily basis between 09:00 and 10:30 for days 2 to 8.

Mesocosm experiment Cape Verde 2012: Environmental conditions (PAR, cloud cover, pump)

Two 7-day mesocosm experiments were conducted in October 2012 at the Instituto Nacional de Desenvolvimento das Pescas (INDP), Mindelo, Cape Verde. Surface water was collected at night before the start of the respective experiment with RV Islândia south of São Vicente (16°44.4'N, 25°09.4'W) and transported to shore using four 600L food safe intermediate bulk containers. Sixteen mesocosm bags were distributed in four flow-through water baths and shaded with blue, transparent lids to approximately 20% of surface irradiation. Mesocosm bags were filled from the containers by gravity, using a submerged hose to minimize bubbles. The accurate volume inside the individual bags was calculated after addition of 1.5 mmol silicate and measuring the resulting silicate concentration. The volume ranged from 105.5 to 145 L. The experimental manipulation comprised addition of different amounts of inorganic N and P. In the first experiment, the P supply was changed at constant N supply in thirteen of the sixteen units, while in the second experiment the N supply was changed at constant P supply in twelve of the sixteen units. In addition to this, "cornerpoints" were chosen that were repeated during both experiments. Four cornerpoints should have been repeated, but setting the nutrient levels in one mesocosm was not succesfull and therefore this mesocosm also was set at the center point conditions. Experimental treatments were evenly distributed between the four water baths. Initial sampling of the mesocosms on day 1 of each run was conducted between 9:45 and 11:30. After nutrient manipulation, sampling was conducted on a daily basis between 09:00 and 10:30 for days 2 to 8.

Ice-rafted debris in ODP Holes 177-1090D and 188-1165B

Constraining the nature of Antarctic Ice Sheet (AIS) response to major past climate changes may provide a window onto future ice response and rates of sea level rise. One approach to tracking AIS dynamics, and differentiating whole system versus potentially heterogeneous ice sheet sector changes, is to integrate multiple climate proxies for a specific time slice across widely distributed locations. This study presents new iceberg-rafted debris (IRD) data across the interval that includes Marine Isotope Stage 31 (MIS 31: 1.081-1.062 Ma, a span of ~19 kyr; Lisiecki and Raymo, 2005), which lies on the cusp of the mid-Brunhes climate transition (as glacial cycles shifted from ~41,000 yr to ~100,000 yr duration). Two sites are studied - distal Ocean Drilling Program (ODP) Leg 177 Site 1090 (Site 1090) in the eastern subantarctic sector of the South Atlantic Ocean, and proximal ODP Leg 188 Site 1165 (Site 1165), near Prydz Bay, in the Indian Ocean sector of the Antarctic margin. At each of these sites, MIS 31 is marked by the presence of the Jaramillo Subchron (0.988-1.072 Ma; Lourens et al., 2004) which provides a time-marker to correlate these two sites with relative precision. At both sites, records of multiple climate proxies are available to aid in interpretation. The presence of IRD in sediments from our study areas, which include garnets indicating a likely East Antarctic Ice Sheet (EAIS) origin, supports the conclusion that although the EAIS apparently withdrew significantly over MIS 31 in the Prydz Bay region and other sectors, some sectors of the EAIS must still have maintained marine margins capable of launching icebergs even through the warmest intervals. Thus, the EAIS did not respond in complete synchrony even to major climate changes such as MIS 31. Further, the record at Site 1090 (supported by records from other subantarctic locations) indicates that the glacial MIS 32 should be reduced to no more than a stadial, and the warm interval of Antarctic ice retreat that includes MIS 31 should be expanded to MIS 33-31. This revised warm interval lasted about 52 kyr, in line with several other interglacials in the benthic d18O records stack of Lisiecki and Raymo (2005), including the super-interglacials MIS 11 (duration of 50 kyr) and MIS 5 (duration of 59 kyr). The record from Antarctica-proximal Site 1165, when interpreted in accord with the record from ANDRILL-1B, indicates that in these southern high latitude sectors, ice sheet retreat and the effects of warming lasted longer than at Site 1090, perhaps until MIS 27. In the current interpretations of the age models of the proximal sites, ice sheet retreat began relatively slowly, and was not really evident until the start of MIS 31. In another somewhat more speculative interpretation, ice sheet retreat began noticeably with MIS 33, and accelerated during MIS 31. Ice sheet inertia (the lag-times in the large-scale responses of major ice sheets to a forcing) likely plays an important part in the timing and scale of these events in vulnerable sectors of the AIS.

Gridded bathymetry from multibeam echosounder EM122 data of the cruise M84/2, off Eregli (2011)

We investigated gas bubble emissions at the Don-Kuban paleo-fan in the northeastern Black Sea regarding their geological setting, quantities as well as spatial and temporal variabilities during three ship expeditions between 2007 and 2011. About 600 bubble-induced hydroacoustic anomalies in the water column (flares) originating from the seafloor above the gas hydrate stability zone (GHSZ) at ~700 m water depth were found. At about 890 m water depth a hydrocarbon seep area named "Kerch seep area" was newly discovered within the GHSZ. We propose locally domed sediments ('mounds') discovered during ultra-high resolution bathymetric mapping with an autonomous underwater vehicle (AUV) to result from gas hydrate accumulation at shallow depths. In situ measurements indicated spatially limited temperature elevations in the shallow sediment likely induced by upward fluid flow which may confine the local GHSZ to a few meters below the seafloor. As a result, gas bubbles are suspected to migrate into near-surface sediments and to escape the seafloor through small-scale faults. Hydroacoustic surveys revealed that several flares originated from a seafloor area of about 1 km**2 in size. The highest flare disappeared in about 350 m water depth, suggesting that the released methane remains in the water column. A methane flux estimate, combining data from visual quantifications during dives with a remotely operated vehicle (ROV) with results from ship-based hydroacoustic surveys and gas analysis revealed that between 2 and 87 x 10**6 mol CH4 yr-1 escaped into the water column above the Kerch seep area. Our results show that the finding of the Kerch seep area represents a so far underestimated type of hydrocarbon seep, which has to be considered in methane budget calculations.

Microbial community, biomarker concentrations and their isotopic signature in sediment of Gullfaks and Tommeliten methane seeps in the Northern North Sea

Gullfaks is one of the four major Norwegian oil and gas fields, located in the northeastern edge of the North Sea Plateau. Tommeliten lies in the greater Ekofisk area in the central North Sea. During the cruises HE 208 and AL 267 several seep locations of the North Sea were visited. At the Heincke seep at Gullfaks, sediments were sampled in May 2004 (HE 208) using a video-guided multiple corer system (MUC; Octopus, Kiel). The samples were recovered from an area densely covered with bacterial mats where gas ebullition was observed. The coarse sands limited MUC penetration depth to maximal 30 centimeters and the highly permeable sands did not allow for a high-resolution, vertical subsampling because of pore water loss. The gas flare mapping and videographic observation at Tommeliten indicated an area of gas emission with a few small patches of bacterial mats with diameters <50 cm from most of which a single stream of gas bubbles emerged. The patches were spaced apart by 10-100 m. Sampling of sediments covered by bacterial mats was only possible with 3 small push cores (3.8 cm diameter) mounted to ROV Cherokee. These cores were sampled in 3 cm intervals. Lipid biomarker extraction from 10 -17 g wet sediment was carried out as described in detail elsewhere (Elvert et al., 2003; doi:10.1080/01490450303894). Briefly, defined concentrations of cholestane, nonadecanol and nonadecanolic acid with known delta 13C-values were added to the sediments prior to extraction as internal standards for the hydrocarbon, alcohol and fatty acid fraction, respectively. Total lipid extracts were obtained from the sediment by ultrasonification with organic solvents of decreasing polarity. Esterified fatty acids (FAs) were cleaved from the glycerol head group by saponification with methanolic KOH solution. From this mixture, the neutral fraction was extracted with hexane. After subsequent acidification, FAs were extracted with hexane. For analysis, FAs were methylated using BF3 in methanol yielding fatty acid methyl esters (FAMES). The fixation for total cell counts and CARD-FISH were performed on-board directly after sampling. For both methods, sediments were fixed in formaldehyde solution. After two hours, aliquots for CARD-FISH staining were washed with 1* PBS (10mmol/l sodium phosphate solution, 130mmol/l NaCl, adjusted to a pH of 7.2) and finally stored in a 1:1 PBS:ethanol solution at -20°C until further processing. Samples for total cell counts were stored in formalin at 4°C until analysis. For sandy samples, the total cell count/CARD-FISH protocol was optimized to separate sand particles from the cells. Cells were dislodged from sediment grains and brought into solution with the supernatant by sonicating each sample onice for 2 minutes at 50W. This procedure was repeated four times and supernatants were combined. The sediment samples were brought to a final dilution of 1:2000 to 1:4000 and filtered onto 0.2µm GTTP filters (Millipore, Eschbonn, Germany).

Seawater carbonate chemistry, calcification and Zn uptake during experiments with coral Stylophora pistillata, 2011

Many studies have investigated the effect of an increase in pCO2 on coral calcification and photosynthesis but the physiological consequences are still relatively speculative. We investigated the effects of ocean acidification on zinc incorporation and gross calcification in the scleractinian coral Stylophora pistillata. Zn is an essential element for health and growth of corals. Colonies were maintained at normal pHT (8.1) and at two low-pH conditions (7.8 and 7.5) during 5 weeks. Corals were exposed to 65Zn dissolved in seawater to assess uptake rates of this element. After 5 weeks, 65Zn activity measured in the whole coral and in the two compartments: tissue and skeleton, differed significantly between pH conditions with concentration factors higher at pHT 8.1, compared to lower pH. Zn is therefore taken less efficiently by corals at reduced pH. Their gross calcification, as measured by 45Ca incorporation, photosynthesis and photosynthetic efficiency did not change with pH even at the lowest level.

Effect of the curing conditions of concrete on the behaviour under freeze-thaw cycles*

The aim of this work is to relate the curing conditions of concrete and the addition of an air-entraining admixture with the damage caused by freeze–thaw cycles. In countries with a continental climate, the curing of concrete in summer is performed under climatic conditions of high temperature and low humidity, and during the winter the concrete suffers conditions of freeze–thaw, often accompanied by the use of de-icing salts. This paper shows the experimental results of the behaviour of concrete specimens cured under climatic summer conditions (high temperature and low humidity) and then subjected to freeze–thaw cycles. Curing of the specimens includes conditions of good and bad practice in relation to wetting and protection of the concrete. It also examines the effectiveness of using an air-entraining admixture in both cases. The experimental programme includes an evaluation of the mechanical properties of the concrete, the study of the cement hydration and the measurement of the volume and pore sizes of the concrete. These tests were performed before and after the application of the freeze–thaw cycles. The results obtained showed that the specimens without air-entraining admixture show a deterioration of mechanical properties after the freeze–thaw test. However, the inclusion of air bubbles benefits the behaviour of concrete against freeze–thaw cycles so even better mechanical properties after the test were observed. This anomalous behaviour is because the cement hydration process continues over the freeze–thaw tests, closing the pore structure. This aspect has been confirmed with the DTA and TG tests performed

Pressure measurements of the detachment bubble on the Bolund Island

Pressure measurements on the surface of a 1:230 scale model of Bolund Island are presented. The model is smooth and no boundary layer generation has been considered since the experiment is designed as the simplest possible reference case. Measurement have been taken for a range of Reynolds numbers based on the average undisturbed wind speed U∞ and the maximum height of the island, h [1.7×104, 8.5×104], and for a range of wind directions. Four minutes time series of pressure in more than 400 points have been acquired and analysed to obtain the spatial distribution of both the time average and the variance of the pressure signal. The horizontal extension of the detachment bubble for the different Reynolds numbers and wind directions is identified by isobars and curves of constant value of pressure variance. The applicability of this technique for evaluating the horizontal topology of high turbulence regions associated to detachment bubbles after escarpments in potential wind farm sites is analysed. The results obtained shows that the behaviour of the mean pressure coefficient, Cp, the std. pressure coefficient, Cp, and the skewness of the pressure, Sp can be used to study the bubble over the island to a certain extent. This experiment is part of the set of different analysis on the Bolund test case that is being undertaken within WAUDIT project by the different scientific groups.

Parallelizing irregular and pointer-based computations automatically: perspectives from logic and constraint programming

Irregular computations pose sorne of the most interesting and challenging problems in automatic parallelization. Irregularity appears in certain kinds of numerical problems and is pervasive in symbolic applications. Such computations often use dynamic data structures, which make heavy use of pointers. This complicates all the steps of a parallelizing compiler, from independence detection to task partitioning and placement. Starting in the mid 80s there has been significant progress in the development of parallelizing compilers for logic pro­gramming (and more recently, constraint programming) resulting in quite capable paralle­lizers. The typical applications of these paradigms frequently involve irregular computations, and make heavy use of dynamic data structures with pointers, since logical variables represent in practice a well-behaved form of pointers. This arguably makes the techniques used in these compilers potentially interesting. In this paper, we introduce in a tutoríal way, sorne of the problems faced by parallelizing compilers for logic and constraint programs and provide pointers to sorne of the significant progress made in the area. In particular, this work has resulted in a series of achievements in the areas of inter-procedural pointer aliasing analysis for independence detection, cost models and cost analysis, cactus-stack memory management, techniques for managing speculative and irregular computations through task granularity control and dynamic task allocation such as work-stealing schedulers), etc.