Hydrate abundances at the high-flux Batumi seep area in the southeastern Black Sea

Submarine gas hydrates are a major global reservoir of the potent greenhouse gas methane. Since current assessments of worldwide hydrate-bound carbon vary by one order of magnitude, new technical efforts are required for improved and accurate hydrate quantifications. Here we present hydrate abundances determined for surface sediments at the high-flux Batumi seep area in the southeastern Black Sea at 840 m water depth using state-of-the art autoclave technology. Pressure sediment cores of up to 2.65 m in length were recovered with an autoclave piston corer backed by conventional gravity cores. Quantitative core degassing yielded volumetric gas/bulk sediment ratios of up to 20.3 proving hydrate presence. The cores represented late glacial to Holocene hemipelagic sediments with the shallowest hydrates found at 90 cmbsf. Calculated methane concentrations in the different cores surpassed methane equilibrium concentrations in the two lowermost lithological Black Sea units sampled. The results indicated hydrate fractions of 5.2% of pore volume in the sapropelic Unit 2 and mean values of 21% pore volume in the lacustrine Unit 3. We calculate that the studied area of ~ 0.5 km**2 currently contains about 11.3 kt of methane bound in shallow hydrates. Episodic detachment and rafting of such hydrates is suggested by a rugged seafloor topography along with variable thicknesses in lithologies. We propose that sealing by hydrate precipitation in coarse-grained deposits and gas accumulation beneath induces detachment of hydrate/sediment chunks. Floating hydrates will rapidly transport methane into shallower waters and potentially to the sea-atmosphere boundary. In contrast, persistent in situ dissociation of shallow hydrates appears unlikely in the near future as deep water warming by about 1.6 °C and/or decrease in hydrostatic pressure corresponding to a sea level drop of about 130 m would be required. Because hydrate detachment should be primarily controlled by internal factors in this area and in similar hydrated settings, it serves as source of methane in shallow waters and the atmosphere which is mainly decoupled from external forcing.

Collection of data on soil carbon (particulate and dissolved) in the Jena Experiment (Main Experiment, time series since 2002)

This data set contains three time series of measurements of soil carbon (particular and dissolved) 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. 1. Particulate soil carbon: Stratified soil sampling was performed every two years since before sowing in April 2002 and was repeated in April 2004, 2006 and 2008 to a depth of 30 cm segmented to a depth resolution of 5 cm giving six depth subsamples per core. Total carbon concentration was analyzed on ball-milled subsamples by an elemental analyzer at 1150°C. Inorganic carbon concentration was measured by elemental analysis at 1150°C after removal of organic carbon for 16 h at 450°C in a muffle furnace. Organic carbon concentration was calculated as the difference between both measurements of total and inorganic carbon. 2. Particulate soil carbon (high intensity sampling): In one block of the Jena Experiment soil samples were taken to a depth of 1 m (segmented to a depth resolution of 5 cm giving 20 depth subsamples per core) with three replicates per block ever 5 years starting before sowing in April 2002. Samples were processed as for the more frequent sampling. 3. Dissolved organic carbon: Suction plates installed on the field site in 10, 20, 30 and 60 cm depth were used to sample soil pore water. Cumulative soil solution was sampled biweekly and analyzed for dissolved organic carbon concentration by a high TOC elemental analyzer. Annual mean values of DOC are provided.

Collection of data on particulate and dissolved soil nitrogen in the Jena Experiment (Main Experiment, time series since 2002)

This data set contains four time series of particulate and dissolved soil nitrogen measurements 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. 1. Total nitrogen from solid phase: Stratified soil sampling was performed every two years since before sowing in April 2002 and was repeated in April 2004, 2006 and 2008 to a depth of 30 cm segmented to a depth resolution of 5 cm giving six depth subsamples per core. In 2002 five samples per plot were taken and analyzed independently. Averaged values per depth layer are reported. In later years, three samples per plot were taken, pooled in the field, and measured as a combined sample. Sampling locations were less than 30 cm apart from sampling locations in other years. All soil samples were passed through a sieve with a mesh size of 2 mm in 2002. In later years samples were further sieved to 1 mm. 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). 2. Total nitrogen from solid phase (high intensity sampling): In block 2 of the Jena Experiment, soil samples were taken to a depth of 1m (segmented to a depth resolution of 5 cm giving 20 depth subsamples per core) with three replicates per block ever 5 years starting before sowing in April 2002. Samples were processed as for the more frequent sampling but were always analyzed independently and never pooled. 3. Mineral nitrogen from KCl extractions: Five soil cores (diameter 0.01 m) were taken at a depth of 0 to 0.15 m (and between 2002 and 2004 also at a depth of 0.15 to 0.3 m) of the mineral soil from each of the experimental plots at various times over the years. In addition also plots of the management experiment, that altered mowing frequency and fertilized subplots (see further details below) were sampled in some later years. Samples of the soil cores per plot (subplots in case of the management experiment) were pooled during each sampling campaign. NO3-N and NH4-N concentrations were determined by extraction of soil samples with 1 M KCl solution and were measured in the soil extract with a Continuous Flow Analyzer (CFA, 2003-2005: Skalar, Breda, Netherlands; 2006-2007: AutoAnalyzer, Seal, Burgess Hill, United Kingdom). 4. Dissolved nitrogen in soil solution: Glass suction plates with a diameter of 12 cm, 1 cm thickness and a pore size of 1-1.6 µm (UMS GmbH, Munich, Germany) were installed in April 2002 in depths of 10, 20, 30 and 60 cm to collect soil solution. The sampling bottles were continuously evacuated to a negative pressure between 50 and 350 mbar, such that the suction pressure was about 50 mbar above the actual soil water tension. Thus, only the soil leachate was collected. Cumulative soil solution was sampled biweekly and analyzed for nitrate (NO3-), ammonium (NH4+) and total dissolved nitrogen concentrations with a continuous flow analyzer (CFA, Skalar, Breda, The Netherlands). Nitrate was analyzed photometrically after reduction to NO2- and reaction with sulfanilamide and naphthylethylenediamine-dihydrochloride to an azo-dye. Our NO3- concentrations contained an unknown contribution of NO2- that is expected to be small. Simultaneously to the NO3- analysis, NH4+ was determined photometrically as 5-aminosalicylate after a modified Berthelot reaction. The detection limits of NO3- and NH4+ were 0.02 and 0.03 mg N L-1, respectively. Total dissolved N in soil solution was analyzed by oxidation with K2S2O8 followed by reduction to NO2- as described above for NO3-. Dissolved organic N (DON) concentrations in soil solution were calculated as the difference between TDN and the sum of mineral N (NO3- + NH4+).

Grain-size distribution, sedimentation rate and x-ray fluorescence data of four sediment cores off the Senegal River estuary

Fine-grained sediment depocenters on continental shelves are of increased scientific interest since they record environmental changes sensitively. A north-south elongated mud depocenter extends along the Senegalese coast in mid-shelf position. Shallow-acoustic profiling was carried out to determine extent, geometry and internal structures of this sedimentary body. In addition, four sediment cores were retrieved with the main aim to identify how paleoclimatic signals and coastal changes have controlled the formation of this mud depocenter. A general paleoclimatic pattern in terms of fluvial input appears to be recorded in this depositional archive. Intervals characterized by high terrigenous input, high sedimentation rates and fine grain sizes occur roughly contemporaneously in all cores and are interpreted as corresponding to intensified river discharge related to more humid conditions in the hinterland. From 2750 to 1900 and from 1000 to 700 cal a BP, wetter conditions are recorded off Senegal, an observation which is in accordance with other records from NW-Africa. Nevertheless, the three employed proxies (sedimentation rate, grain size and elemental distribution) do not always display consistent inter-core patterns. Major differences between the individual core records are attributed to sediment remobilization which was linked to local hydrographic variations as well as reorganizations of the coastal system. The Senegal mud belt is a layered inhomogeneous sedimentary body deposited on an irregular erosive surface. Early Holocene deceleration in the rate of the sea-level rise could have enabled initial mud deposition on the shelf. These favorable conditions for mud deposition occur coevally with a humid period over NW-Africa, thus, high river discharge. Sedimentation started preferentially in the northern areas of the mud belt. During mid-Holocene, a marine incursion led to the formation of an embayment. Afterwards, sedimentation in the north was interrupted in association with a remarkable southward shift in the location of the active depocenter as it is reflected by the sedimentary architecture and confirmed by radiocarbon dates. These sub-recent shifts in depocenters location are caused by migrations of the Senegal River mouth. During late Holocene times, the weakening of river discharge allowed the longshore currents to build up a chain of beach barriers which have forced the river mouth to shift southwards.

Lucky Strike records of hydrothermal outflow temperatures

We deployed autonomous temperature sensors at black smoker chimneys, cracks, and diffuse flow areas at the Lucky Strike hydrothermal field (Mid-Atlantic Ridge, ~37°17'N) between summer 2009 and summer 2012 and contemporaneously measured tidal pressures and currents as part of the long-term MoMAR experiment to monitor hydrothermal activity. We classify the temperature data according to the hydrogeologic setting of the measurement sites: a high-temperature regime (>190°C) representing discharge of essentially unmixed, primary hydrothermal fluids through chimneys, an intermediate-temperature regime (10-100°C) associated with mixing of primary fluids with cold pore fluids discharging through cracks, and a low-temperature regime (<10°C) associated with a thermal boundary layer forming over bacterial mats associated with diffuse outflow of warm fluids. Temperature records from all the regimes exhibit variations at semi-diurnal tidal periods, and cross-spectral analyses reveal that high-temperature discharge correlates to tidal pressure while low-temperature discharge correlates to tidal currents. Intermediate-temperature discharge exhibits a transitional behavior correlating to both tidal pressure and currents. Episodic perturbations, with transient temperature drops of up to ~150°C, which occur in the high-temperature and intermediate-temperature records, are not observed on multiple probes (including nearby probes at the same site), and they are not correlated with microearthquake activity, indicating that the perturbation mechanism is highly localized at the measurement sites within the hydrothermal structures. The average temperature at a given site may increase or decrease at annual time scales, but the average temperature of the hydrothermal field, as a whole, appears to be stable over our 3 year observation period.

(Table 3) Li concentrations and isotopic compositions in foraminiferal shells, carbonate sediments, and associated pore waters from ODP Sites 131-806 and 138-851

An improved procedure for lithium isotope analysis using Li3PO4 as the ion source has been investigated for application to geological samples. The 7Li/6Li ratio is measured using double rhenium filament thermal ionization mass spectrometry in which isotopic fractionation is minimized at high temperatures. The method produces a stable, high intensity Li+ ion beam that allows measurement of nanogram quantities of lithium. This results in a reduction in sample size of up to 1000 times relative to that required for the established Li2BO2+ method while maintaining a comparable precision of better than 1? (1 sigma). Replicate analyses of the NBS L-SVEC Li2CO3 standard yielded a mean value of 12.1047+/-0.0043 (n=21), which is close to the reported absolute value of 12.02+/-0.03. Intercalibration with a wide range of geological samples shows excellent agreement between the Li3PO4 and Li2BO2+ techniques. Replicate analyses of seawater and a fresh submarine basalt display high precision results that agree with previous measurements. Taking advantage of the high ionization efficiency of the phosphate ion source, we have made the first measurements of the lithium concentration (by isotope dilution) and isotopic composition of calcareous foraminiferal tests and other marine carbonates. Preliminary results indicate that substantial lithium exchange occurs between carbonate sediments and their interstitial waters. In addition, a possible link between lithium paleoceanography and paleoclimate during the last 1000 ky may be derived from planktonic foraminiferal tests. This highly sensitive technique can be applied in the examination of low lithium reservoirs and thereby provide insight into some fundamental aspects of lithium geochemistry.

(Table DR1) Biofacies, percentages of important benthic foraminifera and isotope data at ODP Site 758

The Indian monsoon system, as recorded by ocean-floor biota (benthic foraminifera) at Ocean Drilling Program Site 758 in the eastern equatorial Indian Ocean, has varied dramatically over the past 5.5 m.y., long after the onset of the monsoons at 10-8 Ma. Benthic foraminifera that thrive with high productivity year-round were common before the formation of Northern Hemisphere continental ice sheets ca. 3.1-2.5 Ma, indicating that the summer (southwest) monsoon had high intensity and long seasonal duration. Ca. 2.8 Ma benthic faunas became dominated by taxa that flourish with a seasonally strongly fluctuating food supply, indicating that the northeast (winter) monsoon, during which primary productivity is relatively low, increased in duration and strength to form a system similar to that of today. The change occurred coeval with the initiation of the Northern Hemisphere glaciation, documenting a close link between the development of the Indian monsoon and Northern Hemisphere glaciation.

Snow and ice surfaces on King George Island (Antarctic Peninsula) with high-resolution TerraSAR-X time series, with links to shapfiles and GeoTIFFs

Changes of glaciers and snow cover in polar regions affect a wide range of physical and ecosystem processes on land and in the adjacent marine environment. In this study, we investigate the potential of 11-day repeat high-resolution satellite image time series from the TerraSAR-X mission to derive glaciological and hydrological parameters on King George Island, Antarctica during the period Oct/25/2010 to Apr/19/2011. The spatial pattern and temporal evolution of snow cover extent on ice-free areas can be monitored using multi-temporal coherence images. SAR coherence is used to map glacier extent of land terminating glaciers with an average accuracy of 25 m. Multi-temporal SAR color composites identify the position of the late summer snow line at about 220 m above sea level. Glacier surface velocities are obtained from intensity feature-tracking. Surface velocities near the calving front of Fourcade Glacier were up to 1.8 ± 0.01 m/d. Using an intercept theorem based on fundamental geometric principles together with differential GPS field measurements, the ice discharge of Fourcade Glacier was estimated to 20700 ± 5500 m**3/d (corresponding to ~19 ± 5 kt/d). The rapidly changing surface conditions on King George Island and the lack of high-resolution digital elevation models for the region remain restrictions for the applicability of SAR data and the precision of derived products.

A 31,000-year high-resolution record from two sediment cores off northwest Africa

Benthic foraminiferal assemblage compositions and sedimentary geochemical parameters were analyzed in two radiocarbon dated sediment cores from the upwelling area off NW Africa at 12°N, to reconstruct productivity changes during the last 31 kyr. High-latitude cold events and variations in low-latitude summer insolation influenced humidity, wind systems, and the position of the tropical rain belt over this time period. This in turn caused changes in intensity and seasonality of primary productivity off the southern Northwest African continental margin. High accumulation rates of benthic foraminifera, carbonate, and organic carbon during times of north Atlantic melt water events Heinrich 2 (25.4 to 24.3 kyr BP) and 1 (16.8 to 15.8 kyr BP) indicate high productivity. Dominance of infaunal benthic foraminiferal species and high numbers of deep infaunal specimens during that time indicate a strong and sustained supply of refractory organic matter reworked from the upper slope and shelf. A more southerly position of the tropical rainbelt and the Northeast trade wind belt during Heinrich 2 and 1 may have enhanced wind intensity and almost permanent upwelling, driving this scenario. A phytodetritus-related benthic fauna indicates seasonally pulsed input of labile organic matter but generally low year-round productivity during the Last Glacial Maximum (23 to 18 kyr BP). The tropical rainbelt is more expanded to the North than during Heinrich Events, and relatively weak NE trade winds resulted in seasonal and weak upwelling, thus lower productivity. High productivity characterized by a seasonally high input of labile organic matter, is indicated for times of orbital forced warming, such as the African Humid Period (9.8 to 7 kyr BP). An intensified African monsoon during boreal summer and the northernmost position of the tropical rainbelt within the last 31 kyr resulted in enhanced river discharge from the northward-extended drainage area (or river basin) initiating intense phytoplankton blooms. In the late Holocene (4 to 0 kyr BP) strong carbonate dissolution may have been caused by even more enhanced organic matter fluxes to the sea floor. Increasing aridity on the continent and stronger NE trade winds induced intensive, seasonal coastal upwelling.