40Ar-39Ar dating and isotopic composition of groundmass and felspar samples from core AND-2A

The AND-2A drillcore (Antarctic Drilling Program-ANDRILL) was successfully completed in late 2007 on the Antarctic continental margin (Southern McMurdo Sound, Ross Sea) with the aim of tracking ice proximal to shallow marine environmental fluctuations and to document the 20-Ma evolution of the Erebus Volcanic Province. Lava clasts and tephra layers from the AND-2A drillcore were investigated from a petrographic and stratigraphic point of view and analyzed by the 40Ar-39Ar laser technique in order to constrain the age model of the core and to gain information on the style and nature of sediment deposition in the Victoria Land Basin since Early Miocene. Ten out of 17 samples yielded statistically robust 40Ar-39Ar ages, indicating that the AND-2A drillcore recovered <230 m of Middle Miocene (~128-358 m below sea floor, ~11.5-16.0 Ma) and >780 m of Early Miocene (~358-1093 m below sea floor, ~16.0-20.1 Ma). Results also highlight a nearly continuous stratigraphic record from at least 358 m below sea floor down hole, characterized by a mean sedimentation rate of ~19 cm/ka, possible oscillations of no more than a few hundreds of ka and a break within ~17.5-18.1 Ma. Comparison with available data from volcanic deposits on land, suggests that volcanic rocks within the AND-2A core were supplied from the south, possibly with source areas closer to the drill site for the upper core levels, and from 358 m below sea floor down hole, with the 'proto-Mount Morning' as the main source.

Dissolution of a spatially variable DNAPL (dense non aqueous phase liquid) source

Dissolution of non-aqueous phase liquids (NAPLs) or gases into groundwater is a key process, both for contamination problems originating from organic liquid sources, and for dissolution trapping in geological storage of CO2. Dissolution in natural systems typically will involve both high and low NAPL saturations and a wide range of pore water flow velocities within the same source zone for dissolution to groundwater. To correctly predict dissolution in such complex systems and as the NAPL saturations change over time, models must be capable of predicting dissolution under a range of saturations and flow conditions. To provide data to test and validate such models, an experiment was conducted in a two-dimensional sand tank, where the dissolution of a spatially variable, 5x5 cm**2 DNAPL tetrachloroethene source was carefully measured using x-ray attenuation techniques at a resolution of 0.2x0.2 cm**2. By continuously measuring the NAPL saturations, the temporal evolution of DNAPL mass loss by dissolution to groundwater could be measured at each pixel. Next, a general dissolution and solute transport code was written and several published rate-limited (RL) dissolution models and a local equilibrium (LE) approach were tested against the experimental data. It was found that none of the models could adequately predict the observed dissolution pattern, particularly in the zones of higher NAPL saturation. Combining these models with a model for NAPL pool dissolution produced qualitatively better agreement with experimental data, but the total matching error was not significantly improved. A sensitivity study of commonly used fitting parameters further showed that several combinations of these parameters could produce equally good fits to the experimental observations. The results indicate that common empirical model formulations for RL dissolution may be inadequate in complex, variable saturation NAPL source zones, and that further model developments and testing is desirable.

Degradation of [14C]GlcDGD in the marine sediment by monitoring radioactivity in the aqueous and gas phase using liquid scintillation counting (LSC) techniques

An experiment was conceived in which we monitored degradation of GlcDGD. Independent of the fate of the [14C]glucosyl headgroup after hydrolysis from the glycerol backbone, the 14C enters the aqueous or gas phase whereas the intact lipid is insoluble and remains in the sediment phase. Total degradation of GlcDGD then is obtained by combining the increase of radioactivity in the aqueous and gaseous phases. We chose two different sediment to perform this experiment. One is from microbially actie surface sediment sampled in February 2010 from the upper tidal flat of the German Wadden Sea near Wremen (53° 38' 0N, 8° 29' 30E). The other one is deep subsurface sediments recovered from northern Cascadia Margin during Integrated Ocean Drilling Program Expedition 311 [site U1326, 138.2 meters below seafloor (mbsf), in situ temperature 20 °C, water depth 1,828 m. We performed both alive and killed control experiments for comparison. Surface and subsurface sediment slurry were incubated in the dark at in situ temperature, 4 °C and 20 °C for 300 d, respectively. The sterilized slurry was stored at 20 °C. All incubations were carried out under N2 headspace to ensure anaerobic conditions. The sampling frequency was high during the first half-month, i.e., after 1, 2, 7, and 14 d; thereafter, the sediment slurry was sampled every 2 months. At each time point, samples were taken in triplicate for radioactivity measurements. After 300 d of incubation, no significant changes of radioactivity in the aqueous phase were detected. This may be the result of either the rapid turnover of released [14C] glucose or the relatively high limit of detection caused by the slight solubility (equivalent to 2% of initial radioactivity) of GlcDGD in water. Therefore, total degradation of GlcDGD in the dataset was calculated by combining radioactivity of DIC, CH4, and CO2, leading to a minimum estimate.

Chemical composition of hydrothermal sulfide minerals from the Rainbow, Logachev-1, and Logachev-2 hydrothermal fields

Composition of ore minerals in MAR sulflde occurrences related to ultramaflc rocks was studied using methods of mineragraphy, electron microscopy, microprobe analysis, and X-ray analysis. Objects are located at various levels of maturity of sulflde mounds owing to differences in age, duration and degree of activity of the following hydrothermal systems: generally inactive Logatchev-1 field (up to 66.5 ka old), inactive Logatchev-2 field (3.9 ka), and generally active Rainbow field (up to 23 ka). Relative to MAR submarine ore occurrences in the basalt substrate, mineralization in the hydrothermal fields mentioned above is characterized by high contents of Au, Cd, Co, and Ni, along with presence of accessory minerals of Co and Ni. The studied mounds differ in quantitative ratios of major minerals and structural-textural features of ores that suggest their transformation. Ores in the Logatchev-1 field are characterized by the highest Cu content and development of a wide range of multistage contrast exsolution structures of isocubanite and bornite. In the Logatchev-2 field, sphalerite-chalcopyrite and gold-arsenic exsolution structures are present, but isocubanite exsolution structures are less diverse and contrast. The Rainbow field is marked by presence of homogenous isocubanite and the subordinate development of exsolution structures. The authors have identified four new phases in the Cu-Fe-S system. Phases X and Y (close to chalcopyrite and isocubanite, respectively) make up lamellae among isocubanite exsolution products in the Logatchev-1 and Logatchev-2 fields. Phase Y includes homogenous zones in zonal chimneys of the Rainbow field. Phases A and B formed in the orange bornite domain at low-temperature alteration of chalcopyrite in the Logatchev-1 field. Mineral assemblages of the Cu-S system are most abundant and diverse in the Logatchev-1 field, but their development is minimal in the Logatchev-2 field where mainly Cu-poor sulfides of the geerite-covellite series have been identified. Specific features of mineral assemblages mentioned above reflect the maturity grade of sulfide mounds and can serve as indicators of maturity.

Solid phase phosphorus geochemistry in surface sediments of sediment cores GeoB3718-4, GeoB3702-2 and GeoB3707-4

In this study we investigate benthic phosphorus cycling in recent continental margin sediments at three sites off the Namibian coastal upwelling area. Examination of the sediments reveals that organic and biogenic phosphorus are the major P-containing phases preserved. High Corg/Porg ratios just at the sediment surface suggest that the preferential regeneration of phosphorus relative to that of organic carbon has either already occurred on the suspension load or that the organic matter deposited at these sites is already rather refractory. Release of phosphate in the course of benthic microbial organic matter degradation cannot be identified as the dominating process within the observed internal benthic phosphorus cycle. Dissolved phosphate and iron in the pore water are closely coupled, showing high concentrations below the oxygenated surface layer of the sediments and low concentrations at the sediment-water interface. The abundant presence of Fe(III)-bound phosphorus in the sediments document the co-precipitation of both constituents as P-containing iron (oxyhydr)oxides. However, highly dissolved phosphate concentrations in pore waters cannot be explained, neither by simple mass balance calculations nor by the application of an established computer model. Under the assumption of steady state conditions, phosphate release rates are too high as to be balanced with a solid phase reservoir. This discrepancy points to an apparent lack of solid phase phosphorus at sediment depth were suboxic conditions prevail. We assume that the known, active, fast and episodic particle mixing by burrowing macrobenthic organisms could repeatedly provide the microbially catalyzed processes of iron reduction with authigenic iron (oxyhydro)oxides from the oxic surface sediments. Accordingly, a multiple internal cycling of phosphate and iron would result before both elements are buried below the iron reduction zone.

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).

Abundance of mesozooplankton in the western part of the Black Sea in summer 2005 during Phase 2: Leg1 from the GEF Project

The sampling area was extended to the Western-South area off the Black Sea coast from Kaliakra cape toward the Bosforous. Samples were collected along four transects. The whole dataset is composed of 17 samples (from 10 stations) with data of mesozooplankton species composition abundance and biomass. Sampling for zooplankton was performed from bottom up to the surface at depths depending on water column stratification and the thermocline depth. These data are organized in the "Control of eutrophication, hazardous substances and related measures for rehabilitating the Black Sea ecosystem: Phase 2: Leg I: PIMS 3065". Data Report is not published. Zooplankton samples were collected with vertical closing Juday net,diameter - 36cm, mesh size 150 µm. Tows were performed from surface down to bottom meters depths in discrete layers. Samples were preserved by a 4% formaldehyde sea water buffered solution. Sampling volume was estimated by multiplying the mouth area with the wire length. Mesozooplankton abundance: The collected material was analysed using the method of Domov (1959). Samples were brought to volume of 25-30 ml depending upon zooplankton density and mixed intensively until all organisms were distributed randomly in the sample volume. After that 5 ml of sample was taken and poured in the counting chamber which is a rectangle form for taxomomic identification and count. Large (> 1 mm body length) and not abundant species were calculated in whole sample. Counting and measuring of organisms were made in the Dimov chamber under the stereomicroscope to the lowest taxon possible. Taxonomic identification was done at the Institute of Oceanology by Kremena Stefanova using the relevant taxonomic literature (Mordukhay-Boltovskoy, F.D. (Ed.). 1968, 1969,1972). Taxon-specific abundance: The collected material was analysed using the method of Domov (1959). Samples were brought to volume of 25-30 ml depending upon zooplankton density and mixed intensively until all organisms were distributed randomly in the sample volume. After that 5 ml of sample was taken and poured in the counting chamber which is a rectangle form for taxomomic identification and count. Copepods and Cladoceras were identified and enumerated; the other mesozooplankters were identified and enumerated at higher taxonomic level (commonly named as mesozooplankton groups). Large (> 1 mm body length) and not abundant species were calculated in whole sample. Counting and measuring of organisms were made in the Dimov chamber under the stereomicroscope to the lowest taxon possible. Taxonomic identification was done at the Institute of Oceanology by Kremena Stefanova using the relevant taxonomic literature (Mordukhay-Boltovskoy, F.D. (Ed.). 1968, 1969,1972).

(Table 2, page 725) Solid phase chemistry of ferromanganese precipitates from Nova Scotian lakes

Sediments associated with freshwater ferromanganese concretions in Lake Charlotte, Nova Scotia, contained microscopic precipitates of manganese and iron. These precipitates were dispersed throughout the sediment and were as rich in nickel, cobalt, and copper as deep sea concretions. In addition, the development of the precipitates appeared to be associated with the microbial oxidation of manganese. Results from the deployment of poisoned and unpoisoned dialysis probes or peepers demonstrated that microbial manganese oxidation and nickel binding were closely associated, causing a fivefold enhancement of abiotic processes such as adsorption.

Summary of phase compositions of experimental silicate melt, un-normalised analyses

The solubility of Re and Au in haplobasaltic melt has been investigated at 1673-2573 K, 0.1 MPa-2 GPa and IW-1 to +2.5, in both carbon-saturated and carbon-free systems. Results extend the existing, low pressure and temperature, dataset to more accurately predict the results of metal-silicate equilibrium at the base of a terrestrial magma ocean. Solubilities in run-product glasses were measured by laser ablation ICP-MS, which allows for the explicit assessment of contamination by metal inclusions. The Re and Au content of demonstrably contaminant-free glasses increases with temperature, and shows variation with oxygen fugacity (fO2) similar to previous results, although lower valence states for Re (1+, 2+) are suggested by the data. At 2 GPa, and Delta IW of +1.75 to +2, the metal-silicate partition coefficient for Re (DMet/Sil) is defined by the relation LogD[met/sil][Re] = 0.50(±0.022)*10**4/T(K)+3.73(±0.095) For metal-silicate equilibrium to endow Earth's mantle with the observed time-integrated chondritic Re/Os, (and hence 187Os/188Os), DMet/Sil for both elements must converge to a common value. Combined with previously measured DMet/Sil for Os, the estimated temperature at which this convergence occurs is 4500 (±900) K. At this temperature, however, the Re and Os content of the equilibrated silicate is ~100-fold too low to explain mantle abundances. In the same experiments, much lower Dmet/sil values have been determined for Au, and require the metal-silicate equilibration temperature to be <3200 K, as hotter conditions result in an excess of Au in the mantle. Thus, the large disparity in partitioning between Re or Os, and Au at core-forming temperatures argues against their mantle concentrations set solely by metal-silicate equilibrium at the base of a terrestrial magma ocean.

(Table 2) Composition of the deapest pore fluids from ODP Holes 168-1030B and 168-1031A

On the eastern flank of the Juan de Fuca Ridge, reaction between upwelling basement fluid and sediment alters hydrothermal fluxes of Ca, SiO2(aq), SO4, PO4, NH4, and alkalinity. We used the Global Implicit Multicomponent Reactive Transport (GIMRT) code to model the processes occurring in the sediment column (diagenesis, sediment burial, fluid advection, and multicomponent diffusion) and to estimate net seafloor fluxes of solutes. Within the sediment section, the reactions controlling the concentrations of the solutes listed above are organic matter degradation via SO4 reduction, dissolution of amorphous silica, reductive dissolution of amorphous Fe(III)-(hydr)oxide, and precipitation of calcite, carbonate fluorapatite, and amorphous Fe(II)-sulfide. Rates of specific discharge estimated from pore-water Mg profiles are 2 to 3 mm/yr. At this site the basement hydrothermal system is a source of NH4, SiO2(aq), and Ca, and a sink of SO4, PO4, and alkalinity. Reaction within the sediment column increases the hydrothermal sources of NH4 and SiO2(aq), increases the hydrothermal sinks of SO4 and PO4, and decreases the hydrothermal source of Ca. Reaction within the sediment column has a spatially variable effect on the hydrothermal flux of alkalinity. Because the model we used was capable of simulating the observed pore-water chemistry by using mechanistic descriptions of the biogeochemical processes occurring in the sediment column, it could be used to examine the physical controls on hydrothermal fluxes of solutes in this setting. Two series of simulations in which we varied fluid flow rate (1 to 100 mm/yr) and sediment thickness (10 to 100 m) predict that given the reactions modeled in this study, the sediment section will contribute most significantly to fluxes of SO4 and NH4 at slow flow rates and intermediate sediment thickness and to fluxes of SiO2(aq) at slow flow rates and large sediment thickness. Reaction within the sediment section could approximately double the hydrothermal sink of PO4 over a range of flow rates and sediment thickness, and could slightly decrease (by