(Table 2) Methane to ethane ratio, and d13C-methane at DSDP Hole 76-533

Natural gas hydrates are clathrates in which water molecules form a crystalline framework that includes and is stabilized by natural gas (mainly methane) at appropriate conditions of high pressures and low temperatures. The conditions for the formation of gas hydrates are met within continental margin sediments below water depths greater than about 500 m where the supply of methane is sufficient to stabilize the gas hydrate. Observations on DSDP Leg 11 suggested the presence of gas hydrates in sediments of the Blake Outer Ridge. Leg 76 coring and sampling confirms that, indeed, gas hydrates are present there. Geochemical evidence for gas hydrates in sediment of the Blake Outer Ridge includes (1) high concentrations of methane, (2) a sediment sample with thin, matlike layers of white crystals that released a volume of gas twenty times greater than its volume of pore fluid, (3) a molecular distribution of hydrocarbon gases that excluded hydrocarbons larger than isobutane, (4) results from pressure core barrel experiments, and (5) pore-fluid chemistry. The molecular composition of the hydrocarbons in these gas hydrates and the isotopic composition of the methane indicate that the gas is derived mainly from microbiological processes operating on the organic matter within the sediment. Although gas hydrates apparently are widespread on the Blake Outer Ridge, they probably are not of great economic significance as a potential, unconventional, energy resource or as an impermeable cap for trapping upwardly migrating gas at Site 533.

(Appendix) Grain-size distribution, calcium carbonate content and proportion of cemented aggregates in ODP Site 133-820

The textural and compositional characteristics of the 400 m sequence of Pleistocene wackestones and packstones intersected at Ocean Drilling Program (ODP) Site 820 reflect deposition controlled by fluctuations in sea-level, and by variations in the rate of sediment supply. The development of an effective reefal barrier adjacent to Site 820, between 760 k.y. and 1.01 Ma, resulted in a marked reduction in sediment accumulation rates on the central Great Barrier Reef outermost shelf and upper slope. This marked change corresponds with the transition from sigmoidal prograding seismic geometry in the lower 254 m of the sequence, to aggradational geometry in the top 146 m. The reduction in the rate of sediment accumulation that followed development of the reefal barrier also caused a fundamental change in the way in which fluctuations in sea-level controlled sediment deposition. In the lower, progradational portion of the sequence, sea-level cyclicity is represented by superimposed coarsening-upward cycles. Although moderately calcareous throughout (mostly 35%-75% CaCO3), the depositional system acted in a similar manner to siliciclastic shelf depositional systems. Relative sea-level rises resulted in deposition of more condensed, less calcareous, fine, muddy wackestones at the base of each cycle. Sea-level highstands resulted in increased sedimentation rates and greater influx of coarse bioclastic material. Continued high rates of sedimentation of both coarse bioclastic material and mixed carbonate and terrigenous mud marked falling and low sea-levels. This lower part of the sequence therefore is dominated by coarse packstones, with only thin wackestone intervals representing transgressions. In contrast, sea-level fluctuations following formation of an effective reefal barrier produced a markedly different sedimentary record. The more slowly deposited aggradational sequence is characterized by discrete thin interbeds of relatively coarse packstone within a predominantly fine wackestone sequence. These thin packstone beds resulted from relatively low sedimentation rates during falling and low sea-levels, with much higher rates of muddy sediment accumulation during rising and high sea-levels. The transition from progradational to aggradational sequence geometry therefore corresponds to a transition from a "siliciclastic-type" to a "carbonate-type" depositional system.

Mg/Ca ratio, Sr/Ca ratio and stable isotopes of the foraminifera Oridorsalis umbonatus in surface sediment samples

We investigate the influence of carbonate system parameters (carbonate ion concentration, [CO3**2-]; carbonate ion saturation, Delta [CO3**2-]) on the trace element and stable isotope ratios in the endobenthic foraminifera Oridorsalis umbonatus. Data from modern core top samples from the Namibian continental slope suggest that the shell composition of this species is influenced by the chemistry of the pore-water. For these organic-rich sediments, the impact of ocean bottom water properties on both pore-water and shell chemistry is surprisingly small. Sr/Ca correlates positively with [CO3**2-] and to a lesser extent with Delta [CO3**2-], which is opposed to previous results. A [CO3**2-] decrease of 10 µmol/kg leads to an increase of 0.05 mmol/mol in Sr/Ca. We observe a correlation between shell d18O (corrected for temperature and d18O seawater) and [CO3**2-], however, the variability of the corrected d18O is close to the analytical limit. No clear dependences were observed for d13C and Mg/Ca.

Geochemistry, carbon isotope ratio and radiocarbon ages of sediment core GIK1093-2 from Bornholm Basin, Baltic Sea

Concentrations of Cd, Pb, Zn, Cu, Co, Ni, Fe, and Al203, water content, the amounts of organic carbon, the ratio of 13C/12C and the 14C-activity of the organic fraction were determined with sediment depth from a 34 cm long box-core from the Bornholm Basin (Baltic Sea). The average sedimentation rate was 2.4 mm/yr. The upper portion of the core contained increasing amounts of 14C-inactive organic carbon, and above 3 cm depth, man-made 14C from atomic bomb tests. The concentrations of the heavy metals Cd, Pb, Zn, and Cu increase strongly towards the surface, while other metals, as Fe, Ni and Co remain almost unchanged. This phenomenon is attributed to anthropogenic influences. A comparison of the Kieler Bucht, the Bornholm and the Gotland Basins shows that today the anthropogenic addition of Zn is about 100 mg/m**2 yr in all three basins. The beginning of this excess of Zn, however, is delayed by about 20 years in, the Bornholm Basin and by about 40 years in the Gotland Basin. It is suggested that SW-NE transport of these anthropogenically mobilized metals may be related to periodic bottom water renewal in the Baltic Sea sedimentary basins.

Molecular hydrogen (H2) mixing ratio and stable isotopic composition (dD) at the Cabauw tall tower in the Netherlands (2008-2012)

Measurements of the stable isotopic composition (dD(H2) or dD) of atmospheric molecular hydrogen (H2) are a useful addition to mixing ratio (X(H2)) measurements for understanding the atmospheric H2 cycle. dD datasets published so far consist mostly of observations at background locations. We complement these with observations from the Cabauw tall tower at the CESAR site, situated in a densely populated region of the Netherlands. Our measurements show a large anthropogenic influence on the local H2 cycle, with frequently occurring pollution events that are characterized by X(H2) values that reach up to 1 ppm and low dD values. An isotopic source signature analysis yields an apparent source signature below -400 per mil, which is much more D-depleted than the fossil fuel combustion source signature commonly used in H2 budget studies. Two diurnal cycles that were sampled at a suburban site near London also show a more D-depleted source signature (-340 per mil), though not as extremely depleted as at Cabauw. The source signature of the Northwest European vehicle fleet may have shifted to somewhat lower values due to changes in vehicle technology and driving conditions. Even so, the surprisingly depleted apparent source signature at Cabauw requires additional explanation; microbial H2 production seems the most likely cause. The Cabauw tower site also allowed us to sample vertical profiles. We found no decrease in (H2) at lower sampling levels (20 and 60m) with respect to higher sampling levels (120 and 200m). There was a significant shift to lower median dD values at the lower levels. This confirms the limited role of soil uptake around Cabauw, and again points to microbial H2 production during an extended growing season, as well as to possible differences in average fossil fuel combustion source signature between the different footprint areas of the sampling levels. So, although knowledge of the background cycle of H2 has improved over the last decade, surprising features come to light when a non-background location is studied, revealing remaining gaps in our understanding.

Environmental characteristics and gas composition of Lost Hammer, Canadian Arctic

We report the first microbiological characterization of a terrestrial methane seep in a cryo-environment in the form of an Arctic hypersaline (~24% salinity), subzero (-5 C), perennial spring, arising through thick permafrost in an area with an average annual air temperature of -15 C. Bacterial and archaeal 16S rRNA gene clone libraries indicated a relatively low diversity of phylotypes within the spring sediment (Shannon index values of 1.65 and 1.39, respectively). Bacterial phylotypes were related to microorganisms such as Loktanella, Gillisia, Halomonas and Marinobacter spp. previously recovered from cold, saline habitats. A proportion of the bacterial phylotypes were cultured, including Marinobacter and Halomonas, with all isolates capable of growth at the in situ temperature (-5 C). Archaeal phylotypes were related to signatures from hypersaline deep-sea methane-seep sediments and were dominated by the anaerobic methane group 1a (ANME-1a) clade of anaerobic methane oxidizing archaea. CARD-FISH analyses indicated that cells within the spring sediment consisted of ~84.0% bacterial and 3.8% archaeal cells with ANME-1 cells accounting for most of the archaeal cells. The major gas discharging from the spring was methane (~50%) with the low CH4/C2 + ratio and hydrogen and carbon isotope signatures consistent with a thermogenic origin of the methane. Overall, this hypersaline, subzero environment supports a viable microbial community capable of activity at in situ temperature and where methane may behave as an energy and carbon source for sustaining anaerobic oxidation of methane-based microbial metabolism. This site also provides a model of how a methane seep can form in a cryo-environment as well as a mechanism for the hypothesized Martian methane plumes.

Chlorophyll a concentration in plankton, biomass of different taxonomic phytoplankton groups, dominating algae species, and some parameters of coastal surface waters of the Black Sea

Based on data obtained at three stations in coastal waters of the Black Sea off Sevastopol in 2000 and 2001, we present seasonal dynamics of the carbon to chlorophyll a ratio in nano- and microphy-toplankton. This parameter varied approximately tenfold throughout the year. Its maximum values (442-500) were obtained in summer (July), when Pyrrophyta dominated in phytoplankton. Minimum values (36-56) were observed in winter (December),when diatomaceous species predominated. We derive a regression relating the carbon to chlorophyll a ratio to proportion of Pyrrophyta in total phytoplankton biomass, doing so separately for warm and cold seasons. Regression equations demonstrate coupled action of irradiance, temperature, and nutrient availability on the carbon to chlorophyll a ratio. For Pyrrophyta phytoplankton assemblage R**2 = 0.95, and for diatomaceous one R**2 = 0.87.

Total organic carbon, bitumen ratio, hopane and sterane parameters of ODP Sites 128-798 and 128-799

Notable compositional changes of organic matter are observed below the silica transition zone in thermally immature sediments. The increase of bitumen ratio, and hopane and sterane isomerization parameters indicate an acceleration of the kinetics of the chemical reactions which transform the organic matter. This phenomenon is probably due to the numerous mineral and textural changes induced by the transformation of amorphous biogenic silica into crystalline authigenic silica.

Sedimentological and paleoclimatological investigation of two sediment cores off Cape Barbas, North-West Africa

Two box cores taken off Cape Barbas (North-West Africa) have been studied using three methods. The analyses of the coarse fraction, of biogenic opal and of planktonic foraminifera revealed : 1. Core GIK12310-4 penetrates Z, Y, X and upper part of W zone, whereas core GIK12379-1 penetrates Z and upper part of Y zone. 2. Holocene sedimentation rates are 2.5 cm/1000 y for core GIK12310-4 and 6.0 cm/1000 y for core GIK12379-1. During the Y zone 5 cm/l000 y were sedimented incore GIK12310-4 and > 10-20 cm/1000 y in core GIK12379-1. 3. Paleoclimatohgical results are: arid climate and relatively warm water temperatures during the Holocene (Z zone) and during X zone; humid climate and relatively cool water temperatures within the Wuerm (Y zone) (with a non-dated more arid interval found in the middle part of the Y zone) and in the upper part of the W zone. 4. Increased contents of benthos and radiolaria in the Y zone indicate upwelling. Upwelling, characterized by high content of biogenic opal and low water temperatures, was found in core GIK12310-4 at 250 to 350 cm in the lower part of the Y zone. The plankton/benthos ratio of foraminifera, the benthos/radiolaria ratio and water temperatures derived from planktonic foraminifera, differ in both cores in the Holocene, and are nearly identical during the Wuerm.

Lipids in ocean particulate matter and bottom sediments

Lipid contents both in particulate matter and bottom sediments decreases with passage from the shelf toward the open ocean. Lipid concentration in particulate matter collected by a separator (Ls) decreases by a factor of 7 (from 7.05 to 0.95 % of dry matter), while in particulate matter collected on filters (Lf) it decreases by a factor of 13 (from 78 to 6 µg/l) in the vicinity of the Limpopo River and by a factor of 6 (from 74 to 13 µg/l) in the vicinity of the Zambezi River. Concentration of Lf also decreased with depth. In the upper sediment layers lipid concentration was 0.0028-0.039% of dry matter; all mud samples were richer in lipids, than sand samples. During sedimentogenesis there is an increase in proportion of lipids relative to other classes of organic matter, proportion of low-polarity compounds increases among the lipids, and proportion of hydrocarbons rises among these compounds. Sediments inherit composition of particulate matter to the greatest degree in the vicinity of river mouths.

Petrology and geochemistry of basalts from the Vavilov Basin

During ODP Leg 107, two holes were drilled in the basement of Vavilov Basin, a central oceanic area of the Tyrrhenian sea. Hole 655B is located near the Gortani ridge in off-axis position at the western rim of the basin; Hole 651A is located on a basement swell at the axis of the basin. This paper deals with mineral chemistry, major and trace element geochemistry, and petrogenesis of the basalts recovered in the two holes. The mineralogy of the basalts is broadly homogeneous, but all of them have suffered important seawater alteration. Their major-element compositions are similar to both normal-mid-ocean-ridge-basalts (N-MORB) and back-arc-basalts (BAB) except for Na2O contents (BAB-like), and K2O which is somewhat enriched in upper unit of Hole 651 A. Their affinity with N-MORB and BAB is confirmed by using immobile trace elements such as Zr, Y, and Nb. However, basalts from the two sites present contrasting geochemical characteristics on spidergrams using incompatible elements. Hole 655B basalts are homogeneous enriched tholeiites, similar to those from DSDP Hole 373 (located on the opposite side of the basin near the eastern rim), and show affinities with enriched MORB (E-MORB). At Hole 651 A, the two basalt units are chemically distinct. One sample recovered in lower unit is rather similar to those from Hole 655B, but basalts from upper unit display calc-alkaline characteristic evidenced by the increase of light-ion-lithophile-element (LILE)/high-field-strength-element (HFSE) ratio, and appearance of a negative Nb-anomaly, making them comparable with orogenic lavas from the adjacent Eolian arc. The observed chemical compositions of the basalts are consistent with a derivation of the magmas from a N-MORB type source progressively contaminated by LILE-enriched fluids released from dehydration of the bordering subducted plate. Implications for evolution of the Tyrrhenian basin are tentatively proposed taking into consideration geochemical and chronological relationships between basalts from Leg 107 Holes 655B and 651 A, together with data from Leg 42 Site 373 and Vavilov Seamount. These data illustrate back-arc spreading in ensialic basin closely associated with the maturation of the adjacent subduction, followed by the growth of late off-axis central volcano, whereas the active subduction retreats southeastward.