(Table 1) Total organic carbon, calcium carbonate and nitrogen at DSDP Holes 80-559 and 80-550B

Concentrations of organic and inorganic nitrogen have been measured on Leg 80 sediments. The inorganic nitrogen content is relatively constant, 0.02-0.03 wt.%. Because most of the inorganic nitrogen occurs as NH3 or (NH4)+ fixed on clays, clay-poor sediments have lower inorganic nitrogen contents. Organic nitrogen content depends upon both the type and the quantity of organic matter present. In Leg 80 sediments, woody kerogens contain much less organic nitrogen than do kerogens of algal origin. Furthermore, pelagic samples of low organic carbon content have less organic nitrogen than predicted, because of loss during diagenesis. DSDP shipboard analytical procedures do not distinguish between organic and inorganic nitrogen. Great caution must therefore be exercised in interpreting C/N ratios.

Chemistry and fluid inclusions of the sheeted dike comples of ODP Holes 137-504B and 140-504B

Fluid inclusions in variably altered diabase recovered from Ocean Drilling Program Legs 137 and 140 at Hole 504B, Costa Rica Rift, exhibit fluid salinities up to 3.7 times that of seawater values (11.7 wt% NaCl equivalent) and exhibit uncorrected homogenization temperatures of 125°C to 202°C. The liquid-dominated inclusions commonly are entrapped in zones of secondary plagioclase and may be primary in origin. Fluid salinities are similar to compositions of fluids venting on the seafloor (0.4-7.0 wt% NaCl) and overlap with those measured in metabasalt samples recovered from near the Kane Fracture Zone on the Mid-Atlantic Ridge and from the Troodos ophiolite, Cyprus. The salinity variations may reflect hydration reactions involving formation of secondary mineral assemblages under rock-dominated conditions, which modify the ionic strength of hydrothermal fluids by consuming or liberating water and chloride ion. Rare CO2-CH4-bearing inclusions, subjacent to zones where talc after olivine becomes an important secondary mineral phase (1700 mbsf), may have formed due to local interaction of seawater and olivine at low water to rock ratios. Corrected average fluid inclusion homogenization temperatures exhibit a gradient from 159°C at a depth of 1370 mbsf to 183°C at a depth of 1992 mbsf and are in apparent equilibrium with the present conductive downhole temperatures. These data indicate that fluid inclusions may be used to estimate downhole temperatures if logging data are unavailable. The compositional and thermal evolution of the diabase-hosted fluids may reflect late-stage, off-axis circulation and conductive heating of compositionally modified seawater in the sheeted dike complex at Hole 504B.

Carbon dioxide assimilation rate, gas and ion composition in samples, and bacterial production of organic matter within and above the Broken Spur and TAG hydrothermal fields, Mid-Atlantic Ridge

Rate of CO2 assimilation was determined above the Broken Spur and TAG active hydrothermal fields for three main ecosystems: (1) hydrothermal vents; (2) 300 m near-bottom layer of plume water; and (3) bottom sediments. In water samples from warm (40-45°C) vents assimilation rates were maximal and reached 2.82-3.76 µg C/l/day. In plume waters CO2 assimilation rates ranged from 0.38 to 0.65 µg C/l/day. In bottom sediments CO2 assimilation rates varied from 0.8 to 28.0 µg C/l/day, rising up to 56 mg C/kg/day near shrimp swarms. In the most active plume zone of the long-living TAG field bacterial production of organic matter (OM) from carbonic is up to 170 mg C/m**2/day); production of autotrophic process of bacterial chemosynthesis reaches about 90% (156 mg C/m**2/day). Thus, chemosynthetic production of OM in September-October is almost equal to that of photosynthetic production in the oceanic region. Bacterial production of OM above the Broken Spur hydrothermal field is one order lower and reaches only 20 mg C/m**2/day.

Helium isotope ratios and pore gases in deep-sea sediments of the Japan Sea

We have measured the 3He/4He and 4He/20Ne ratios and chemical compositions of gases exsolved from deep-sea sediments at two sites (798 and 799) in the Japan Sea. The 3He/4He and 4He/20Ne ratios vary from 0.642 Ratm (where Ratm is the atmospheric 3He/4He ratio of 1.393*10**-6) to 0.840 Ratm, and from 0.41 to 4.5, respectively. Helium in the samples can be explained by the mixing between atmospheric helium dissolved in bottom water of the Japan Sea and crustal helium in the sediment. The sedimentary helium is enriched in mantle-derived 3He compared with those from the Japan Trench and the Nankai Trough. This suggests that the basement of the Japan Sea has relatively large remnants of mantle-derived helium compared with that of the Pacific. Major chemical compositions of the samples are methane and nitrogen. There is a positive correlation between methane content and helium content corrected for air component. Based on the 3He/4He-Sum C/3He diagram, the major part of methane can be attributed to crustal and/or organic origin.

Phytoplankton and bacterial productivity in the Tugur Bay (Sea of Okhotsk) in July-August 1990

A study of quantitative characteristics: phytoplankton photosynthesis (Ph), bacterial assimilation of CO2 (BA), total abundance of bacteria (TAB) and organic matter destruction (D) was carried out in waters the Tugur Bay (tidal level fluctuations up to 7 m) in July-August 1990. Calculations were made of integral indices in some parts: Ph -10-630, BA - 8-29, D - 280-1015 and of total primary production (TPP) - 18-652 mg C/(m2 day). According to obtained data and TAB the ecosystem of the Tugur Bay can be regarded as oligotrophic-mesotrophic one. Dependence on spatial and temporal inhomogeneity of primary productional processes on tide-ebb cycles was found. The role of bacterial relations in the ecosystem of the bay was shown. Portion of ?A in TPP varied from 4 to 44% reaching the maximum in desalinated water during the tide-ebb.

Stable carbon and oxygen isotope ratios of bulk sediment from DSDP Hole 62-463 (Appendix A)

In order to elucidate early Aptian marine paleotemperature evolution across the period of enhanced organic carbon (Corg)-burial [Oceanic Anoxic Event (OAE) 1a], stable isotope analyses were performed on pelagic limestones at Deep Sea Drilling Project Site 463, central Pacific Ocean. The delta18O data exhibit a distinct anomaly by ~-2? spanning the OAE 1a interval (i.e., a ~6 m-thick, phytoplanktonic Corg-rich unit constrained by magneto-, bio- and delta13C stratigraphy). Elucidation of paleotemperature significance of the delta18O shift is made by taking account of recent Sr/Ca evidence at the same section, which revealed that geochemical signals in carbonate-poor lithologies are relatively unaltered against burial diagenesis. By discriminating delta18O values from carbonate-poor samples (CaCO3 contents=5-30 wt.%), it appears that an abrupt rise in seasurface temperatures (SSTs) by 8 °C (=-1.7? shift in delta18O) occurred immediately before OAE 1a, whereas a cooling mode likely prevailed during the peak Corg-burial. In terms of its stratigraphic relationship as to the Corg-rich interval and to a pronounced negative delta13C excursion, as well as its timescale, the observed SST rise resembles those associated with the Paleocene-Eocene thermal maximum and, more strikingly, Jurassic Toarcian OAE. This observation is consistent with the hypothesis that these paleoenvironmental events were driven by a common causal mechanism, which was likely initiated by the greenhouse effect via massive release of CH4 or CO2 from the isotopically-light carbon reservoir and terminated by a negative productivity feedback.

Concentrations and isotopic compositions of low molecular weight hydrocarbons in hydrothermal fluids from ODP Field, Middle Valley, northern Juan de Fuca Ridge

The presence of sedimentary organic matter blanketing midocean ridge crests has a potentially strong impact on metal transport in hydrothermal vent fluids. To constrain the role of organic matter in metal mobility during hydrothermal sediment alteration, we reacted organic-rich diatomaceous ooze from Guaymas Basin, Gulf of California, and organic-poor hemipelagic mud from Middle Valley, northern Juan de Fuca Ridge, with seawater and a Na-Ca-K-Cl fluid of seawater chlorinity, at 275° to 400°C, 350 to 500 bars, and initial fluid: sediment mass ratios ranging from 1.6 to 9.8. Reaction of these fluids with both sediment types released CO2 and high concentrations of ore-forming metals (Fe, Mn, Zn, Pb) to solution. Relatively low concentrations of Cu were observed in solution and likely reflect the reducing conditions that resulted from the presence of sedimentary organic matter. Both the concentrations of CO2 and dissolved metals were lower in fluids reacted with Middle Valley sediment compared with aqueous concentrations in fluids reacted with Guaymas Basin sediment. During alteration of both sediment types, metal concentrations varied strongly as a function of temperature, increasing by up to an order of magnitude over the 75°C range of each experiment. Major element fluid chemistry and observed alteration assemblages suggest that during hydrothermal alteration of organic-lean sediment from Middle Valley a feldspar-quartz-illite mineral assemblage buffered in situ pH. In contrast, data from the experimental alteration of organic-rich Guaymas Basin sediment suggest that a calcite-plagioclase-quartz assemblage regulated in situ pH. Fluid speciation calculations suggest that in situ pH during Guaymas Basin sediment alteration was lower than during alteration of Middle Valley sediment and accounts for the substantially greater metal mobility at a given temperature and pressure during the former experiment. Comparison of our results with the results of basalt alteration experiments indicate that except for Cu, hydrothermal sediment alteration results in equal or greater concentrations of ore-forming metals at a given temperature and pressure. Accordingly, the presence of ore-forming metals in fluids currently venting from sediment-covered hydrothermal systems at concentrations substantially lower than in fluids from bare-rock systems may reflect chemical reequilibration during subsurface cooling within the sediment pile.

Organic and inorganic geochemistry and archaeal community composition of hypersaline sediments from Orca Basin, RV Atlantis Expedition AT18-02

Among the most extreme habitats on Earth, dark, deep, anoxic brines host unique microbial ecosystems that remain largely unexplored. As the terminal step of anaerobic degradation of organic matter, methanogenesis is a potentially significant but poorly constrained process in deep-sea hypersaline environments. We combined biogeochemical and phylogenetic analyses as well as incubation experiments to unravel the origin of methane in hypersaline sediments of Orca Basin in the northern Gulf of Mexico. Substantial concentrations of methane (up to 3.4 mM) coexisted with high concentrations of sulfate (16-43 mM) in two sediment cores retrieved from the northern and southern parts of Orca Basin. The strong depletion of 13C in methane (-77 to -89 per mill) pointed towards a biological source. While low concentrations of competitive substrates limited the significance of hydrogenotrophic and acetoclastic methanogenesis, the presence of non-competitive methylated substrates (methanol, trimethylamine, dimethyl sulfide, dimethylsulfoniopropionate) supported the potential for methane generation through methylotrophic methanogenesis. Thermodynamic calculations demonstrated that hydrogenotrophic and acetoclastic methanogenesis were unlikely to occur under in situ conditions, while methylotrophic methanogenesis from a variety of substrates was highly favorable. Likewise, carbon isotope relationships between methylated substrates and methane supported methylotrophic methanogenesis as the major source of methane. Stable isotope tracer and radiotracer experiments with 13C bicarbonate, acetate and methanol as well as 14C-labeled methylamine indicated that methylotrophic methanogenesis was the predominant methanogenic pathway. Based on 16S rRNA gene sequences, halophilic methylotrophic methanogens related to the genus Methanohalophilus dominated the benthic archaeal community in the northern basin but also occurred in the southern basin. High abundances of methanogen lipid biomarkers such as intact polar and polyunsaturated hydroxyarchaeols were detected in sediments from the northern basin, with lower abundances in the southern basin. Strong 13C-depletion of saturated and monounsaturated hydroxyarchaeol were consistent with methylotrophic methanogenesis as the major methanogenic pathway. Collectively, the availability of methylated substrates, thermodynamic calculations, experimentally determined methanogenic activity as well as lipid and gene biomarkers strongly suggested methylotrophic methanogenesis as predominant pathway of methane formation in the presence of sulfate in Orca Basin sediments.

Temperature, salinity, methane concentration, oxidation rates and methanotrophic cell number at Svalbard seeps in summer 2011 and 2012 (cruises POS419 and MSM21/4)

Large amounts of the greenhouse gas methane are released from the seabed to the water column where it may be consumed by aerobic methanotrophic bacteria. This microbial filter is consequently the last marine sink for methane before its liberation to the atmosphere. The size and activity of methanotrophic communities, which determine the capacity of the water column methane filter, are thought to be mainly controlled by nutrient and redox dynamics, but little is known about the effects of ocean currents. Here, we report measurements of methanotrophic activity and biomass (CARD-FISH) at methane seeps west of Svalbard, and related them to physical water mass properties (CTD) and modelled current dynamics. We show that cold bottom water containing a large number of aerobic methanotrophs was rapidly displaced by warmer water with a considerably smaller methanotrophic community. This water mass exchange, caused by short-term variations of the West Spitsbergen Current, constitutes a rapid oceanographic switch severely reducing methanotrophic activity in the water column. Strong and fluctuating currents are widespread oceanographic features common at many methane seep systems and are thus likely to globally affect methane oxidation in the ocean water column.

Methane and stable isotope record of ice core EDML from Dronning Maud Land, Antarctica

Precise knowledge of the phase relationship between climate changes in the two hemispheres is a key for understanding the Earth's climate dynamics. For the last glacial period, ice core studies have revealed strong coupling of the largest millennial-scale warm events in Antarctica with the longest Dansgaard-Oeschger events in Greenland through the Atlantic meridional overturning circulation. It has been unclear, however, whether the shorter Dansgaard-Oeschger events have counterparts in the shorter and less prominent Antarctic temperature variations, and whether these events are linked by the same mechanism. Here we present a glacial climate record derived from an ice core from Dronning Maud Land, Antarctica, which represents South Atlantic climate at a resolution comparable with the Greenland ice core records. After methane synchronization with an ice core from North Greenland, the oxygen isotope record from the Dronning Maud Land ice core shows a one-to-one coupling between all Antarctic warm events and Greenland Dansgaard-Oeschger events by the bipolar seesaw. The amplitude of the Antarctic warm events is found to be linearly dependent on the duration of the concurrent stadial in the North, suggesting that they all result from a similar reduction in the meridional overturning circulation.

Pore water and solid-phase data from site Scharendijke (Lake Grevelingen, NL)

Will be submitted by the author

Isotopes content, mineralogical composition, Uranium and Thorium contents and determined activity ratios from METEOR cruise M74/3 in 2007

Authigenic carbonate deposits have been sampled with the remotely operated vehicle 'MARUM-QUEST 4000 m' from five methane seeps between 731 and 1823 m water depth along the convergent Makran continental margin, offshore Pakistan (northern Arabian Sea). Two seeps on the upper slope are located within the oxygen minimum zone (OMZ; ca. 100 to 1100 m water depth), the other sites are situated in oxygenated water below the OMZ (below 1100 m water depth). The carbonate deposits vary with regard to their spatial extent, sedimentary fabrics, and associated seep fauna: Within the OMZ, carbonates are spatially restricted and associated with microbial mats, whereas in the oxygenated zone below the OMZ extensive carbonate crusts are exposed on the seafloor with abundant metazoans (bathymodiolin mussels, tube worms, galatheid crabs). Aragonite and Mg-calcite are the dominant carbonate minerals, forming common early diagenetic microcrystalline cement and clotted to radial-fibrous cement. The delta18O carbonate values range from 1.3 to 4.2 per mil V-PDB, indicating carbonate precipitation at ambient bottom-water temperature in shallow sediment depth. Extremely low delta13Ccarbonate values (as low - 54.6per mil V-PDB) point to anaerobic oxidation of methane (AOM) as trigger for carbonate precipitation, with biogenic methane as dominant carbon source. Prevalence of biogenic methane in the seepage gas is corroborated by delta13C methane values ranging from - 70.3 to - 66.7per mil V-PDB, and also by back-calculations considering delta 13C methane values of carbonate and incorporated lipid biomarkers.

The Lena River Delta - Land cover classification of tundra environments based on Landsat 7 ETM+ data and its application for upscaling of methane emissions

The Lena River Delta, situated in Northern Siberia (72.0 - 73.8° N, 122.0 - 129.5° E), is the largest Arctic delta and covers 29,000 km**2. Since natural deltas are characterised by complex geomorphological patterns and various types of ecosystems, high spatial resolution information on the distribution and extent of the delta environments is necessary for a spatial assessment and accurate quantification of biogeochemical processes as drivers for the emission of greenhouse gases from tundra soils. In this study, the first land cover classification for the entire Lena Delta based on Landsat 7 Enhanced Thematic Mapper (ETM+) images was conducted and used for the quantification of methane emissions from the delta ecosystems on the regional scale. The applied supervised minimum distance classification was very effective with the few ancillary data that were available for training site selection. Nine land cover classes of aquatic and terrestrial ecosystems in the wetland dominated (72%) Lena Delta could be defined by this classification approach. The mean daily methane emission of the entire Lena Delta was calculated with 10.35 mg CH4/m**2/d. Taking our multi-scale approach into account we find that the methane source strength of certain tundra wetland types is lower than calculated previously on coarser scales.

Isotopic data of atmospheric methane from EDML and Vostok ice cores over a full glacial cycle

The response of natural CH4 sources to climate changes will be an important factor to consider as concentrations of this potent greenhouse gas continue to increase. Polar ice cores provide the means to assess this sensitivity in the past and have shown a close connection between CH4 levels and northern hemisphere temperature variability over the last glacial cycle. However, the contribution of the various CH4 sources and sinks to these changes is still a matter of debate. Contemporaneous stable CH4 isotope records in ice cores provide additional boundary conditions for assessing changes in the CH4 sources and sinks. Here we present new ice core CH4 isotope data covering the last 160,000 years, showing a clear decoupling between CH4 loading and carbon isotopic variations over most of the record. We suggest that d13CH4 variations were not dominated by a change in the source mix but rather by climate- and CO2-related ecosystem control on the isotopic composition of the methane precursor material, especially in seasonally inundated wetlands in the tropics. In contrast, relatively stable d13CH4 intervals occurred during large CH4 loading changes concurrently with past climate changes implying that most CH4 sources (most notably tropical wetlands) responded simultaneously.