Bitumoids and methane in bottom sediments of the northeast Black Sea

Complex investigations of recent and ancient Black Sea sediments from the outer shelf, continental slope, and deep-water basin of the Russian Black Sea sector have been carried out. Samples were collected during Cruise 100 of R/V Professor Shtokman organized by the P.P. Shirshov Institute of Oceanology (March 2009) and expedition of UZHMORGEO (summer 2006). Rates of the main anaerobic processes during diagenesis (sulfate reduction, dark CO2 assimilation, methanogenesis, and methane oxidation) were studied for the first time in sediment cores of the studied area. Two peaks in the rate of microbial processes and two sources of these processes were identified: the upper peak near the water-sediment contact is related to solar energy (OM substrate of the water column) and the lower peak at the base of ancient Black Sea sediments with high(>1 mmol) methane concentration related to energy of anaerobic methane oxidation. New labile OM formed during this process is utilized by other groups of microorganisms. According to experimental data, daily rate of anaerobic methane oxidation is many times higher than that of methanogenesis, which unambiguously indicates migration nature of the main part of methane.

Age models, ostracods and trace elements of five gravity cores from the NW Black Sea

New Mg/Ca, Sr/Ca, and published stable oxygen isotope and 87Sr/86Sr data obtained on ostracods from gravity cores located on the northwestern Black Sea slope were used to infer changes in the Black Sea hydrology and water chemistry for the period between 30 to 8 ka B.P. (calibrated radiocarbon years). The period prior to 16.5 ka B.P. was characterized by stable conditions in all records until a distinct drop in d18O values combined with a sharp increase in 87Sr/86Sr occurred between 16.5 and 14.8 ka B.P. This event is attributed to an increased runoff from the northern drainage area of the Black Sea between Heinrich Event 1 and the onset of the Bølling warm period. While the Mg/Ca and Sr/Ca records remained rather unaffected by this inflow; they show an abrupt rise with the onset of the Bølling/Allerød warm period. This rise was caused by calcite precipitation in the surface water, which led to a sudden increase of the Sr/Ca and Mg/Ca ratios of the Black Sea water. The stable oxygen isotopes also start to increase around 15 ka B.P., although in a more gradual manner, due to isotopically enriched meteoric precipitation. While Sr/Ca remains constant during the following interval of the Younger Dryas cold period, a decrease in the Mg/Ca ratio implies that the intermediate water masses of the Black Sea temporarily cooled by 1-2°C during the Younger Dryas. The 87Sr/86Sr values drop after the cessation of the water inflow at 15 ka B.P. to a lower level until the Younger Dryas, where they reach values similar to those observed during the Last Glacial Maximum. This might point to a potential outflow to the Mediterranean Sea via the Sea of Marmara during this period. The inflow of Mediterranean water started around 9.3 ka B.P., which is clearly detectable in the abruptly increasing Mg/Ca, Sr/Ca, and 87Sr/86Sr values. The accompanying increase in the d18O record is less pronounced and would fit to an inflow lasting ~100 a.

(Table 1) Heat flow data in the western Black Sea

Results of heat flow measurements are presented. On the basis of new data on structure of the sedimentary sequence, corrections are introduced that take account of effect of sedimentation. Diagrammatic maps of distribution of observed and deep-seated heat flow have been constructed. A hypothesis is offered that the regional zone of anomalously high heat-flow values on the northern continental slope has been controlled by processes of subsidence of an oceanic plate beneath its continental counterpart.

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.

Distribution of planktonic foraminifera in Pleistocene sediments of the New Jersey margin, NW Atlantic Ocean

Abundance records of planktonic foraminifera (>150 µm) from the upper 520 m of ODP Site 1073 (Hole 1073A, Leg 174A, 639 m water depth) have been integrated with SPECMAP-derived isotope stratigraphy, percentage of calcium carbonate, and coarse sediment fraction data in order to investigate the Pleistocene climatic history of the New Jersey margin. Six planktonic taxonomic groups dominate the foraminiferal assemblage at Site 1073: Neogloboquadrina pachyderma (d) (mean 33.8%), Turborotalita quinqueloba (18.5%), N. pachyderma (s) (18.4%), Globigerina bulloides group (11.4%), Globorotalia inflata group (9.4%), and Globigerinita glutinata (4.1%). Based on the distributions of these six foraminiferal groups, the Pleistocene section can be divided into three paleoclimatic intervals: Interval I (intermediate) corresponds to the Quaternary sediments from sequence boundary pp1 to the seafloor (79.5-0 mbsf; Emiliania huxleyi acme [85 ka] at 72 mbsf); Interval II (warm) occurs between sequence boundaries pp3 and pp1 (325-79.5 mbsf; last occurrence of Pseudoemiliania lacunosa [460 ka] at 330 mbsf); and Interval III (coldest) occurs between sequence boundaries pp4 and pp3 (520-325 mbsf; Calcareous nannofossils and dinocysts in proximity to pp4 indicate that the sedimentary record for 0.9-1.7 Ma is either missing altogether or highly condensed within the basal few meters of the section). Neogloboquadrina pachyderma (d) displays eight peaks of abundance which correlate, for the most part, with depleted delta18O values, increases in calcium carbonate percentages, low coarse fraction percentages, increased planktonic fragmentation (greater dissolution), and low N. pachyderma (s) abundances. These intervals are interpreted as representing warmer/interglacial conditions. Neogloboquadrina pachyderma (s) displays seven peaks of abundance which correlate, for the most part, with delta18O increases, decreases in calcium carbonate percentages, increases in coarse fraction percentages, and low N. pachyderma (d) abundances. These intervals are interpreted as representing cooler/glacial conditions. In Interval III, a faunal response to relative changes in sea-surface temperature is reflected by abundance peaks in Neogloboquadrina pachyderma (d), followed by Turborotalita quinqueloba and then N. pachyderma (s) (proceeding from warmest to coolest, respectively). This tripartite response is consistent with the oxygen isotope record and, although not as clear, also occurs in Intervals I and II. Six peaks/peak intervals of Globigerina bulloides abundance are closely matched by peaks in Globigerinita glutinata and occur within oxygen isotope stage (OIS) 2 (latter part) 3, 4, 5, 8, 9, 13(?), 14(?), and 15(?). We speculate that these intervals reflect increased upwelling and nutrient levels during both glacials and interglacials. Eight peak intervals of Globorotalia inflata show a general inverse correlation with G. bulloides and may reflect lowered nutrient and warmer surface waters.

Composition and fluxes of sinking particulate material and bottom sediments in the northeast Black Sea in 1998-1999

For the first time deep-sea mooring stations with sediment traps were deployed in the northeast Black Sea. One sediment trap for long-term studies was located at Station 1 (44°15'N, 37°43'E, deployment depth 1800 m, depth 1900 m). The trap collected sinking sedimentary material from January to May 1998. Material collectors were changed every 15 days. Other stations with sediment traps for short-term studies (September-October 1999) were located on the shelf: Station 2 (44°16'N, 38°37'E, deployment depth 45 m, depth 50 m) and on the bottom of the canyon: Station 3 (44°16'N, 38°22'E, deployment depth 1145 m, depth 1150 m), Station 4 (44°11'N, 38°21'E, deployment depths 200, 1550, 1650 m, depth 1670 m). Collected material indicates that vertical particle fluxes are controlled by seasonal changes of in situ production and by dynamics of terrigenous matter input. Higher vertical particle flux of carbonate and biogenic silica was in spring due to bloom of plankton organisms. Maximum of coccolith bloom is in April-May. Bloom of diatoms begins in March. In winter and autumn lithogenic material dominates in total flux. Its amount strongly depends on storms and river run-off. Suspended particle material differs from surface shelf sediments by finer particles (mainly clay fraction) and high content of clay minerals and biogenic silica. This material may form lateral fluxes with higher concentration of particles transported along the bottom of deep-sea canyons from the shelf to the deep basin within the nepheloid layer. In winter such transportation of sedimentary material is more intensive due to active vertical circulation of water masses.

Stable isotope geochemistry of pore waters and marine sediments from the New Jersey shelf: Methane formation and fluid origin

Interstitial water and sediment samples of the Integrated Ocean Drilling Program (IODP) expedition 313 "New Jersey Shallow Shelf" were analyzed for chemical composition and stable isotope ratios. A total of 222 water samples were collected from the cores by Rhizon samplers and squeezing of fresh core material. Water was analyzed for its stable oxygen and hydrogen isotope geochemistry (d2H and d18O) at sites M0027A and M0029A, and the carbon isotope composition of the dissolved inorganic carbon (d13CDIC) (all sites). In addition, organic material (Corg) and inorganic carbonates from sediments were analyzed for their carbon ratios (d13Corg and d13Ccarb), and in case of the carbonates also for oxygen (d18Ocarb). Carbon isotopes were also analyzed in samples containing enough methane gas (d13Cmeth). Pore fluids from site M0027A were analyzed for the sulfur isotope composition of dissolved sulfate (d34S). The combination of isotope analyses of all phases (interstitial water, sediment, and gas) with pore water chemistry is expected to enable a better understanding of processes in the sediment and will help to identify the origin of fluids under the New Jersey shelf.

Stable carbon and oxygen isotope record of diagenetic carbonates from the New Jersey shelf

Carbon cycling is an important but poorly understood process on passive continental margins. In this study, we use the ionic and stable isotopic composition of interstitial waters and the petrology, mineralogy, and stable isotopic composition of authigenic carbonates collected from Ocean Drilling Program (ODP) Leg 174A (Sites 1071 and 1072) to constrain the origin of the carbonates and the evolution of methane on the outer New Jersey shelf. The pore fluids of the New Jersey continental shelf are characterized by (1) a fresh-brackish water plume, and (2) organic matter degradation reactions, which proceed through sulfate reduction. However, only minor methanogenesis occurs. The oxygen isotopic composition of the pore fluids supports a meteoric origin of the low salinity fluids. Authigenic carbonates are found in nodules, thin (~1-cm) layers, and carbonate cemented pavements. Siderite is the most common authigenic carbonate, followed by dolomite and calcite. The oxygen isotopic composition of the authigenic carbonates, i.e. 1.3-6.5 per mil PeeDee Belemnite (PDB), indicates an origin in marine pore fluids. The carbon isotopic composition of dolomite cements range from -16.4 to -8.8 per mil PDB, consistent with formation within the zone of sulfate reduction. Siderite d13C values show a greater range (-17.67-16.4 per mil), but are largely positive (mean=2.8 per mil) and are interpreted to have formed throughout the zone of methanogenesis. In contrast, calcite d13C values are highly negative (as low as -41.7 per mil)and must have formed from waters with a large component of dissolved inorganic carbon derived from methane oxidation. Pore water data show that despite complete sulfate reduction, methanogenesis appears not to be an important process presently occurring in the upper 400 m of the outer New Jersey shelf. In contrast, the carbon isotopic composition of the siderites and calcites document an active methanogenic zone during their formation. The methane may have been either oxidized or vented from shelf sediments, perhaps during sea-level fluctuations. If this unaccounted and variable methane flux is an areally important process during Neogene sea-level fluctuations, then it likely plays an important role in long-term carbon cycling on passive continental margins

Abundance and biomass of mesozooplankton in the western Black sea during Steaua de Mare cruise in 1982 and 1983

The Poluare 1982-1983 dataset contains zooplankton data collected allong 7 transect in front of the Romanian littoral. Zooplankton sampling was undertaken at 14 stations where samples were collected using a Juday closing net in the 0-2m layer . The dataset includes samples analysed for mesozooplankton species composition and abundance. Sampling volume was estimated by multiplying the mouth area with the wire length. Total biomass was estimated using a tabel with wet weight for each species an stage. Taxon-specific mesozooplankton abundance was counted under the microscope.

Stable carbon isotope record of benthic foraminifera across the Paleocene-Eocene thermal maximum in the New Jersey Coastal Plain

In the New Jersey Coastal Plain, a silty to clayey sedimentary unit (the Marlboro Formation) represents deposition during the Paleocene-Eocene thermal maximum (PETM). This interval is remarkably different from the glauconitic sands and silts of the underlying Paleocene Vincentown and overlying Eocene Manasquan Formation. We integrate new and published stable isotope, biostratigraphic, lithostratigraphic and ecostratigraphic records, constructing a detailed time frame for the PETM along a depth gradient at core sites Clayton, Wilson Lake, Ancora and Bass River (updip to downdip). The onset of the PETM, marked by the base of the carbon isotope excursion (CIE), is within the gradual transition from glauconitic silty sands to silty clay, and represented fully at the updip sites (Wilson Lake and Clayton). The CIE "core" interval is expanded at the updip sites, but truncated. The CIE "core" is complete at the Bass River and Ancora sites, where the early part of the recovery is present (most complete at Ancora). The extent to which the PETM is expressed in the sediments is highly variable between sites, with a significant unconformity at the base of the overlying lower Eocene sediments. Our regional correlation framework provides an improved age model, allowing better understanding of the progression of environmental changes during the PETM. High-resolution benthic foraminiferal data document the change from a sediment-starved shelf setting to a tropical, river-dominated mud-belt system during the PETM, probably due to intensification of the hydrologic cycle. The excellent preservation of foraminifera during the PETM and the lack of severe benthic extinction suggest there was no extreme ocean acidification in shelf settings.

Investigations on seven sediment cores from the New Ireland Basin, east of Papua New Guinea

Sediment cores were recovered from the New Ireland Basin, east of Papua New Guinea, in order to investigate the late Quaternary eruptive history of the Tabar-Lihir-Tanga-Feni (TLTF) volcanic chain. Foraminifera d18O profiles were matched to the low-latitude oxygen isotope record to date the cores, which extend back to the early part of d18O Stage 9 (333 ka). Sedimentation rates decrease from >10 cm/1000 yr in cores near New Ireland to ~2 cm/1000 yr further offshore. The cores contain 36 discrete ash beds, mostly 1-8 cm thick and interpreted as either fallout or distal turbidite deposits. Most beds have compositionally homogeneous glass shard populations, indicating that they represent single volcanic events. Shards from all ash beds have the subduction-related pattern of strong enrichment in the large-ion lithophile elements relative to MORB, but three distinct compositional groups are apparent: Group A beds are shoshonitic and characterised by >1300 ppm Sr, high Ce/Yb and high Nb/Yb relative to MORB, Group B beds form a high-K series with MORB-like Nb/Yb but high Ce/Yb and well-developed negative Eu anomalies, whereas Group C beds are transitional between the low-K and medium-K series and characterised by flat chondrite-normalised REE patterns with low Nb/Yb relative to MORB. A comparison with published data from the TLTF chain, the New Britain volcanic arc and backarc including Rabaul, and Bagana on Bougainville demonstrates that only Group A beds share the distinctive phenocryst assemblage and shoshonitic geochemistry of the TLTF lavas. The crystal- and lithic-rich character of the Group A beds point to a nearby source, and their high Sr, Ce/Yb and Nb/Yb match those of Tanga and Feni lavas. A youthful stratocone on the eastern side of Babase Island in the Feni group is the most probable source. Group A beds younger than 20 ka are more fractionated than the older Group A beds, and record the progressive development of a shallow level magma chamber beneath the cone. In contrast, Group B beds represent glass-rich fallout from voluminous eruptions at Rabaul, whereas Group C beds represent distal glass-rich fallout from elsewhere along the volcanic front of the New Britain arc.

Sediment and organic matter properties, and molecular formula from sampling locations in the Northern Black Sea

Remineralization of organic matter in reactive marine sediments releases nutrients and dissolved organic matter (DOM) into the ocean. Here we focused on the molecular-level characterization of DOM by high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) in sediment pore waters and bottom waters from contrasting redox regimes in the northern Black Sea with particular emphasis on nitrogen-bearing compounds to derive an improved understanding of the molecular transformations involved in nitrogen release. The number of nitrogen-bearing molecules is generally higher in pore waters than in bottom waters. This suggests intensified degradation of nitrogen-bearing precursor molecules such as proteins in anoxic sediments: No significant difference was observed between sediments deposited under oxic vs anoxic conditions (average O/C ratios of 0.55) suggesting that the different organic matter quality induced by contrasting redox conditions does not impact protein diagenesis in the subseafloor. Compounds in the pore waters were on average larger, less oxygenated, and had a higher number of unsaturations. Applying a mathematical model, we could show that the assemblages of nitrogen-bearing molecular formulas are potential products of proteinaceous material that was transformed by the following reactions: (a) hydrolysis and deamination, both reducing the molecular size and nitrogen content of the products and intermediates; (b) oxidation and hydration of the intermediates; and (c) methylation and dehydration.

Latest Cretaceous to Late Paleocene radiolarian biostratigraphy from the New Zealand region

The scarcity of records of Early Paleocene radiolarians has meant that while radiolarian biostratigraphy is firmly established as an important tool for correlation, there has been a long-standing gap between established zonations for the Cretaceous and from latest Paleocene to Recent. It has also led to considerable speculation over the level of faunal change across the Cretaceous/Tertiary (K/T) boundary. Consequently, the discovery of rich and diverse radiolarian assemblages in well-delineated K/T boundary sections within siliceous limestones of the Amuri Limestone Group in eastern Marlborough, New Zealand, is of great significance for biostratigraphy and K/T boundary research. This initial report is restricted to introducing a new latest Cretaceous to mid Late Paleocene zonation based on the radiolarian succession at four of these sections and a re-examination of faunas from coeval sediments at DSDP Site 208 (Lord Howe Rise). Three new Paleocene species are described: Amphisphaera aotea, Amphisphaera kina and Stichomitra wero. Six new interval zones are defined by the first appearances of the nominate species. In ascending order these are: Lithomelissa? hoplites Foreman (Zone RK9, Cretaceous), Amphisphaera aotea n. sp. (Zone RP1, Paleocene), Amphisphaera kina n. sp. (RP2), Stichomitra granulata Petrushevskaya (RP3), Buryellaforemanae petrushevskaya (RP4) and Buryella tetradica (RP5). Good age control from foraminifera and calcareous nannofossils permits close correlation with established microfossil zonations. Where age control is less reliable, radiolarian events are used to substantially improve correlation between the sections. No evidence is found for mass extinction of radiolarians at the end of the Cretaceous. However, the K/T boundary does mark a change from nassellarian to spumellarian dominance, due to a sudden influx of actinommids, which effectively reduces the relative abundance of many Cretaceous survivors. An accompanying influx of diatoms in the basal Paleocene of Marlborough, together with evidence for an increase of total radiolarian abundance, suggests siliceous plankton productivity increased across the K/T boundary. Possible causes for this apparently localised phenomenon are briefly discussed.

The new DGFI-TUM realization of the ITRS: DTRF2014 (data)

The DTRF2014 is a realization of the the fundamental Earth-fixed coordinate system, the International Terrestrial Reference System (ITRS). It has been computed by the Deutsches Geodätisches Forschungsinstitut der Technischen Universität München (DGFI-TUM). The DTRF2014 consists of station positions and velocities of 1712 globally distributed geodetic observing stations of the observation techniques VLBI, SLR, GNSS and DORIS. Additionally, for the first time, non-tidal atmospheric and hydrological loading is considered in the solution. The DTRF2014 was released in August 2016 and incorporates observation data of the four techniques up 2014. The observation data were processed and submitted by the corresponding technique services: IGS (International GNSS Service, http://igscb.jpl.nasa.gov) IVS (International VLBI Service, http://ivscc.gsfc.nasa.gov) ILRS (International Laser Ranging Service, http://ilrs.gsfc.nasa.gov) IDS (International DORIS Service, http://ids-doris.org). The DTRF2014 is an independent ITRS realization. It is computed on the basis of the same input data as the realizations JTRF2014 (JPL, Pasadena) and ITRF2014 (IGN, Paris). The three realizations of the ITRS differ conceptually. While DTRF2014 and ITRF2014 are based on station positions at a reference epoch and velocities, the JTRF2014 is based on time series of station positions. DTRF2014 and ITRF2014 result from different combination strategies: The ITRF2014 is based on the combination of solutions, the DTRF2014 is computed by the combination of normal equations. The DTRF2014 comprises 3D coordinates and coordinate changes of 1347 GNSS-, 113 VLBI-, 99 SLR- and 153 DORIS-stations. The reference epoch is 1.1.2005, 0h UTC. The Earth Orientation Parameters (EOP) - that means the coordinates of the terrestrial and the celestial pole, UT1-UTC and the Length of Day (LOD) - were simultaneously estimated with the station coordinates. The EOP time series cover the period from 1979.7 to 2015.0. The station names are the official IERS identifiers: CDP numbers or 4-character IDs and DOMES numbers (http://itrf.ensg.ign.fr/doc_ITRF/iers_sta_list.txt). The DTRF2014 solution is available in one comprehensive SINEX file and four technique-specific SINEX files, see below. A detailed description of the solution is given on the website of DGFI-TUM (http://www.dgfi.tum.de/en/science-data-products/dtrf2014/). More information can be made available by request.