High-resolution in situ oxygen microprofiles, porewater and solid phase geochemistry from the Crimean shelf (Black Sea) from Maria S. Merian cruise MSM15/1

The outer western Crimean shelf of the Black Sea is a natural laboratory to investigate effects of stable oxic versus varying hypoxic conditions on seafloor biogeochemical processes and benthic community structure. Bottom-water oxygen concentrations ranged from normoxic (175 µmol O2/L) and hypoxic (< 63 µmol O2/L) or even anoxic/sulfidic conditions within a few kilometers' distance. Variations in oxygen concentrations between 160 and 10 µmol/L even occurred within hours close to the chemocline at 134 m water depth. Total oxygen uptake, including diffusive as well as fauna-mediated oxygen consumption, decreased from 15 mmol/m**2/d on average in the oxic zone, to 7 mmol/m**2/d on average in the hypoxic zone, correlating with changes in macrobenthos composition. Benthic diffusive oxygen uptake rates, comprising respiration of microorganisms and small meiofauna, were similar in oxic and hypoxic zones (on average 4.5 mmol/m**2/d), but declined to 1.3 mmol/m**2/d in bottom waters with oxygen concentrations below 20 µmol/L. Measurements and modeling of porewater profiles indicated that reoxidation of reduced compounds played only a minor role in diffusive oxygen uptake under the different oxygen conditions, leaving the major fraction to aerobic degradation of organic carbon. Remineralization efficiency decreased from nearly 100 % in the oxic zone, to 50 % in the oxic-hypoxic zone, to 10 % in the hypoxic-anoxic zone. Overall, the faunal remineralization rate was more important, but also more influenced by fluctuating oxygen concentrations, than microbial and geochemical oxidation processes.

High-resolution pore-water and solid-phase analyses of sediment cores GeoB6520-3 (Hydrate Hole) and GeoB6521-2 (Worm Hole) of the northern Congo Fan

The geochemical cycling of barium was investigated in sediments of pockmarks of the northern Congo Fan, characterized by surface and subsurface gas hydrates, chemosynthetic fauna, and authigenic carbonates. Two gravity cores retrieved from the so-called Hydrate Hole and Worm Hole pockmarks were examined using high-resolution pore-water and solid-phase analyses. The results indicate that, although gas hydrates in the study area are stable with respect to pressure and temperature, they are and have been subject to dissolution due to methane-undersaturated pore waters. The process significantly driving dissolution is the anaerobic oxidation of methane (AOM) above the shallowest hydrate-bearing sediment layer. It is suggested that episodic seep events temporarily increase the upward flux of methane, and induce hydrate formation close to the sediment surface. AOM establishes at a sediment depth where the upward flux of methane from the uppermost hydrate layer counterbalances the downward flux of seawater sulfate. After seepage ceases, AOM continues to consume methane at the sulfate/methane transition (SMT) above the hydrates, thereby driving the progressive dissolution of the hydrates "from above". As a result the SMT migrates downward, leaving behind enrichments of authigenic barite and carbonates that typically precipitate at this biogeochemical reaction front. Calculation of the time needed to produce the observed solid-phase barium enrichments above the present-day depths of the SMT served to track the net downward migration of the SMT and to estimate the total time of hydrate dissolution in the recovered sediments. Methane fluxes were higher, and the SMT was located closer to the sediment surface in the past at both sites. Active seepage and hydrate formation are inferred to have occurred only a few thousands of years ago at the Hydrate Hole site. By contrast, AOM-driven hydrate dissolution as a consequence of an overall net decrease in upward methane flux seems to have persisted for a considerably longer time at the Worm Hole site, amounting to a few tens of thousands of years.

Age determinations and sedimentology on cores GIK17940 and 184-1144

Sedimentological, geochemical and paleomagnetic records were employed to reconstruct the history of East Asian Monsoon variability in the South China Sea (SCS) on orbital- and millennial-to-sub-decadal time scales. A detailed magnetostratigraphy for the southern central SCS was established as well as a stable isotope stratigraphy for ODP Site 1144 for the last 1.2 million years in the northern South China Sea. Furthermore a volcanic tephra layer from the southern central SCS could be identified as the Youngest Toba Ash, which thus re-presents an important age marker and was used to reconstruct paleo wind directions during the eruption 74 ka. Special attention was paid to the high- and ultrahigh-frequency variability in the last glacial-interglacial cycle and the Holocene, and to a precise age control of climate changes in general.

(Table 3) Run conditions and phase relations and proportions during cooling rate experiments on ODP Interval 163-989B-10R-7,55-59

Equilibrium melting and controlled cooling experiments were undertaken to constrain the crystallization and cooling histories of tholeiitic basalts recovered by the Ocean Drilling Program drilling of Site 989 on the Southeast Greenland continental margin. Isothermal experiments conducted at 1 atm. and at the fayalite-magnetite-quartz buffer using lava sample Section 163-989B-10R-7 yielded the equilibrium appearance sequence with decreasing temperature: olivine at 1184 ± 2ºC; plagioclase at 1177ºC ± 5ºC; augite at 1167 ± 5ºC; and pigeonite at 1113 ± 12ºC. In controlled cooling experiments using the same starting composition and cooling rates between 10ºC/hr and 2000ºC/hr, we find a significant temperature delay in the crystallization of olivine, plagioclase, and augite (relative to the equilibrium appearance temperature); pigeonite does not form under any dynamic crystallization conditions. Olivine exhibits the largest suppression in appearance temperature (e.g., 30º for 10ºC/hr and >190º at 100ºC/hr), while plagioclase shows the smallest (~10ºC at 10ºC/hr; 30ºC at 100ºC/hr, and ~80ºC at 1000ºC/hr). These results are in marked contrast to those obtained on lunar basalts, which generally show a large suppression of plagioclase crystallization and modest suppression of olivine crystallization with an increased cooling rate. The results we report agree well with the petrography of lavas recovered from Site 989. Furthermore, the textural analysis of run products, representing a large range of cooling rates and quench temperatures (1150ºC to 1000ºC), provide a framework for evaluating cooling conditions necessary for glass formation, rates of plagioclase growth, and kinetic factors governing plagioclase growth morphology. Specifically, we use these insights to interpret the textural and mineralogical features of the unusual compound flow recovered at Site 989. We concluded from the analysis that this flow most likely records multiple breakouts from a distal tube at an abrupt break in slope, possibly a fault scarp, resulting in the formation of a lava fan delta. This interpretation implies that normal faulting of the oldest lava sequences (lower and, possibly, middle series) preceded eruption of Site 989 lavas.

Hydrate, ice and quartz content of eight holes of Leg 204

The state of preservation of natural gas hydrate samples, recovered from 6 sites drilled during ODP Leg 204 at southern summit of Hydrate Ridge, Oregon Margin, has been investigated by X-ray diffraction (XRD) and cryo-scanning-electron-microscopy (cryo-SEM) techniques. A detailed characterization of the state of decomposition of gas hydrates is necessary since no pressurized autoclave tools were used for sampling and partial dissociation must have occurred during recovery prior to the quench and storage in liquid nitrogen. Samples from 16 distinct horizons have been investigated by synchrotron X-ray diffraction measurements at HASYLAB/ Hamburg. A full profile fitting analysis ("Rietveld method") of synchrotron XRD data provides quantitative phase determinations of the major sample constituents such as gas hydrate structure I (sI), hexagonal ice (Ih) and quartz. The ice content (Ih) in each sample is related to frozen water composed of both original existing pore water and the water from decomposed hydrates. Hydrate contents as measured by diffraction vary between 0 and 68 wt.% in the samples we measured. Samples with low hydrate content usually show micro-structural features in cryo-SEM ascribed to extensive decomposition. Comparing the appearance of hydrates at different scales, the grade of preservation seems to be primarily correlated with the contiguous volume of the original existing hydrate; the dissociation front appears to be indicated by micrometer-sized pores in a dense ice matrix.

Total nitrogen from solid phase in the Jena Experiment (Main Experiment up to 30cm depth, year 2008)

This data set contains measurements of total nitrogen from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Soil sampling and analysis: Stratified soil sampling was performed in April 2008 to a depth of 30 cm. Three independent samples per plot were taken using a split tube sampler with an inner diameter of 4.8 cm (Eijkelkamp Agrisearch Equipment, Giesbeek, the Netherlands). Soil samples were segmented to a depth resolution of 5 cm in the field, giving six depth subsamples per core, and made into composite samples per depth. Sampling locations were less than 30 cm apart from sampling locations in other years. Samples were dried at 40°C. All soil samples were passed through a sieve with a mesh size of 2 mm. Because of much higher proportions of roots in the soil, the samples were further sieved to 1 mm according to common root removal methods. No additional mineral particles were removed by this procedure. Total nitrogen concentration was analyzed on ball-milled subsamples (time 4 min, frequency 30 s-1) by an elemental analyzer at 1150°C (Elementaranalysator vario Max CN; Elementar Analysensysteme GmbH, Hanau, Germany).

Total nitrogen from solid phase in the Jena Experiment (Block 2 Main Experiment up to 100cm depth, year 2002)

This data set contains measurements of total nitrogen from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Soil sampling and analysis: Stratified soil sampling to a depth of 1m was performed before sowing in April 2002. Three independent samples per plot were taken of all plots in block 2 using a motor-driven soil column cylinder (Cobra, Eijkelkamp, 8.3 cm in diameter). Soil samples were dried at 40°C and segmented to a depth resolution of 5 cm giving 20 depth subsamples per core. All samples were analyzed independently. All soil samples were passed through a sieve with a mesh size of 2 mm. Rarely present visible plant remains were removed using tweezers. Total nitrogen concentration was analyzed on ball-milled subsamples (time 4 min, frequency 30 s-1) by an elemental analyzer at 1150°C (Elementaranalysator vario Max CN; Elementar Analysensysteme GmbH, Hanau, Germany).

Total nitrogen from solid phase in the Jena Experiment (Main Experiment up to 30cm depth, year 2004)

This data set contains measurements of total nitrogen from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Soil sampling and analysis: Stratified soil sampling was performed in April 2004 to a depth of 30 cm. Three independent samples per plot were taken using a split tube sampler with an inner diameter of 4.8 cm (Eijkelkamp Agrisearch Equipment, Giesbeek, the Netherlands). Soil samples were segmented to a depth resolution of 5 cm in the field, giving six depth subsamples per core, and made into composite samples per depth. Sampling locations were less than 30 cm apart from sampling locations in other years. Samples were dried at 40°C. All soil samples were passed through a sieve with a mesh size of 2 mm. Because of much higher proportions of roots in the soil, the samples were further sieved to 1 mm according to common root removal methods. No additional mineral particles were removed by this procedure. Total nitrogen concentration was analyzed on ball-milled subsamples (time 4 min, frequency 30 s-1) by an elemental analyzer at 1150°C (Elementaranalysator vario Max CN; Elementar Analysensysteme GmbH, Hanau, Germany).

Age determinations on 4 sediment cores off Iceland

The north Icelandic shelf is partly distinguished by the Tjörnes Fracture Zone featuring numerous active basins in a mud-dominated shelf environment. Late Glacial and Holocene high-resolution sedimentary records from this area have been studied with tephrochronology as the main tool for correlation and for exact timing of palaeoceanographic events in the area. Data from three new piston cores from the shelf demonstrate the importance of tephra markers for the first chronological evaluation and correlation of the cores. The correlation is extended with lithological logs and with magnetic susceptibility records. A detailed multidisciplinary study (including biostratigraphy and tephrochronology) of a late Holocene record of predominantly muddy sediments at the same location demonstrates that marked variations in the distribution of water masses occurred repeatedly through the last 4500 cal. yr. Of special interest is the exact timing of a marked drop in sea-surface temperature in the area, indicated by ice rafting debris concentration, to about 50 years before the Hekla 3 eruption, which occurred at 2980 cal. yr BP. This appears to predate most records of a general cooling event in NW Europe by a couple of centuries. Two different possible age models, one based on 14C dates combined with tephra markers and one based on tephra markers alone, are discussed in context with the problem of different marine reservoir ages of the water masses in the area.

Age determinations of sediment cores from the Baffin Shelf

Cores HU82-034-057 and HU84-035-008, Resolution Basin, SE Baffin Shelf, contain 200 and 450 cm, respectively, of sediment that spans the Younger Dryas chron. In both cores the interval is bracketed by 14C dates on foraminifera or molluscs. These sites were close to the margin of the late Wisconsin (Foxe) ice sheet as it flowed toward the Labrador Sea. Prior to 11 ka, both cores record moderate to high accumulations of foraminifera, relatively high del 18O values in planktonic foraminifera, and low values of detrital carbonate. The diatom and percent opal records imply occasional seasonally open water conditions. During part of the Younger Dryas chron both the diatom and opal analyses imply a shutoff of biogenic silica production, suggesting surface water conditions affected by increased sea ice and/or reduced nutrients. In addition, the Younger Dryas interval is marked by an increase in coarse sand and detrital carbonate, a decrease in total organic carbon and foraminifera, and high rates of sediment accumulation. The inferred environment during the Younger Dryas is ice-proximal. In HU82-034-057, the foraminifera and other data suggest a change in conditions during the middle part of the Younger Dryas chron.

Pore water concentrations and solid phase concentrations of sediment cores from the Ligurian continental slope

In October 1979, a period of heavy rainfall along the French Riviera was followed by the collapse of the Ligurian continental slope adjacent to the airport of Nice, France. A body of slope sediments, which was shortly beforehand affected by construction work south of the airport, was mobilized and traveled hundreds of kilometers downslope into the Var submarine canyon and, eventually, into the deep Ligurian basin. As a direct consequence, the construction was destroyed, seafloor cables were torn, and a small tsunami hit Antibes shortly after the failure. Hypotheses regarding the trigger mechanism include (i) vertical loading by construction of an embankment south of the airport, (ii) failure of a layer of sensitive clay within the slope sequence, and (iii) excess pore fluid pressures from charged aquifers in the underground. Over the previous decades, both the sensitive clay layers and the permeable sand and gravel layers were sampled to detect freshened waters. In 2007, the landslide scar and adjacent slopes were revisited for high-resolution seafloor mapping and systematic sampling. Results from half a dozen gravity and push cores in the shallow slope area reveal a limited zone of freshening (i.e. groundwater influence). A 100-250 m wide zone of the margin shows pore water salinities of 5-50% SW concentration and depletion in Cl, SO4, but Cr enrichment, while cores east or west of the landslide scar show regular SW profiles. Most interestingly, the three cores inside the landslide scar hint towards a complex hydrological system with at least two sources for groundwater. The aquifer system also showed strong freshening after a period of several months without significant precipitation. This freshening implies that charged coarse-grained layers represent a permanent threat to the slope's stability, not just after periods of major rainfall such as in October 1979.

Calcium isotope ratios of pore fluids and solid phase of organic rich sediments

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (d44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of d44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, d44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the d44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.

Age determinations of rocks from Vestfjella and Ahlmannryggen in Antarctica

The Proterozoic country rock at Ahlmannryggen consists of flat lying basaltic lo andesitic lava flows and sedimentary rocks intruded by dioritic sills (Borgmassivet Intrusives). The suites display a typical platform cover. K-Ar age determinations gave maximum ages of about 1200 Ma on the magmatic rocks. All these suites were intruded bv Proterozoic dikes dated also at about 1200 Ma. Localiy the Proterozoic rocks have a slaty cleavage grading into mylonitic texture which strike parallel to the Jutul Penck graben. Such tectonic structures were dated at 525 Ma using syntectonic white micas. Evidence of the break-up of Gondwana during the Early Jurassic/Triassic is given by dikes at Ahlmannryggen and lava flows, dikes and sills at Vestfjella. At Ahlmannryggen the initial rift phase is documented by the development of the Jutul Penck graben and the intrusion of the 200-250 Ma continental-tholeiitic dikes striking parallel to the graben axis. The lava flows, dikes and sills at Vestfjella represent a later stage of the Gondwana break-up at about 180 Ma that probably reflects the initial stage of the opening of the Weddell Sea.