Molecular and isotopic characteristics of gas hydrate-bound hydrocarbons in southern and central Lake Baikal

We investigated the molecular composition (methane, ethane, and propane) and stable isotope composition (methane and ethane) of hydrate-bound gas in sediments of Lake Baikal. Hydrate-bearing sediment cores were retrieved from eight gas seep sites, located in the southern and central Baikal basins. Empirical classification of the methane stable isotopes (δ¹³C and δD) for all the seep sites indicated the dominant microbial origin of methane via methyl-type fermentation; however, a mixture of thermogenic and microbial gases resulted in relatively high methane δ¹³C signatures at two sites where ethane δ¹³C indicated a typical thermogenic origin. At one of the sites in the southern Baikal basin, we found gas hydrates of enclathrated microbial ethane in which ¹³C and deuterium were both highly depleted (mean δ¹³C and δD of –61.6‰ V-PDB and –285.4‰ V-SMOW, respectively). To the best of our knowledge, this is the first report of C₂ δ¹³C–δD classification for hydrate-bound gas in either freshwater or marine environments.     

Distribution and expression of gas seeps in a gas hydrate province of the northeastern Sakhalin continental slope, Sea of Okhotsk

Multidisciplinary surveys were conducted to investigate gas seepage and gas hydrate accumulation on the northeastern Sakhalin continental slope (NESS), Sea of Okhotsk, during joint Korean–Russian–Japanese expeditions conducted from 2003 to 2007 (CHAOS and SSGH projects). One hundred sixty-one gas seeps were detected in a 2000 km² area of the NESS (between 53°45′N and 54°45′N). Active gas seeps in a gas hydrate province on the NESS were evident from features in the water column, on the seafloor, and in the subsurface: well-defined hydroacoustic anomalies (gas flares), side-scan sonar structures with high backscatter intensity (seepage structures), bathymetric structures (pockmarks and mounds), gas- and gas-hydrate-related seismic features (bottom-simulating reflectors, gas chimneys, high-amplitude reflectors, and acoustic blanking), high methane concentrations in seawater, and gas hydrates in sediment near the seafloor. These expressions were generally spatially related; a gas flare would be associated with a seepage structure (mound), below which a gas chimney was present. The spatial distribution of gas seeps on the NESS is controlled by four types of geological structures: faults, the shelf break, seafloor canyons, and submarine slides. Gas chimneys that produced enhanced reflection on high-resolution seismic profiles are interpreted as active pathways for upward gas migration to the seafloor. The chimneys and gas flares are good indicators of active seepage.     

Diverse Range of Mineralization Induced by Phase Separation of Hydrothermal Fluid: Case Study of the Yonaguni Knoll IV Hydrothermal Field in the Okinawa Trough Back-Arc Basin

The Yonaguni Knoll IV hydrothermal vent field (24°51′N, 122°42′E) is located at water depths of 1370–1385 m near the western edge of the southern Okinawa Trough. During the YK03–05 and YK04–05 expeditions using the submersible Shinkai 6500, both hydrothermal precipitates (sulfide/sulfate/carbonate) and high temperature fluids (Tmax = 328°C) presently venting from chimney‐mound structures were extensively sampled. The collected venting fluids had a wide range of chemistry (Cl concentration 376–635 mmol kg^?1), which is considered as evidence for sub‐seafloor phase separation. While the Cl‐enriched smoky black fluids were venting from two adjacent chimney‐mound structures in the hydrothermal center, the clear transparent fluids sometimes containing CO₂ droplet were found in the peripheral area of the field. This distribution pattern could be explained by migration of the vapor‐rich hydrothermal fluid within a porous sediment layer after the sub‐seafloor phase separation. The collected hydrothermal precipitates demonstrated a diverse range of mineralization, which can be classified into five groups: (i) anhydrite‐rich chimneys, immature precipitates including sulfide disseminations in anhydrite; (ii) massive Zn‐Pb‐Cu sulfides, consisting of sphalerite, wurtzite, galena, chalcopyrite, pyrite, and marcasite; (iii) Ba‐As chimneys, composed of barite with sulfide disseminations, sometimes associated with realgar and orpiment overgrowth; (iv) Mn‐rich chimneys, consisting of carbonates (calcite and magnesite) and sulfides (sphalerite, galena, chalcopyrite, alabandite, and minor amount of tennantite and enargite); and (v) pavement, silicified sediment including abundant native sulfur or barite. Sulfide/sulfate mineralization (groups i–iii) was found in the chimney–mound structure associated with vapor‐loss (Cl‐enriched) fluid venting. In contrast, the sulfide/carbonate mineralization (group iv) was specifically found in the chimneys where vapor‐rich (Cl‐depleted) fluid venting is expected, and the pavement (group v) was associated with diffusive venting from the seafloor sediment. This correspondence strongly suggests that the subseafloor phase separation plays an important role in the diverse range of mineralization in the Yonaguni IV field. The observed sulfide mineral assemblage was consistent with the sulfur fugacity calculated from the FeS content in sphalerite/wurtzite and the fluid temperature for each site, which suggests that the shift of the sulfur fugacity due to participation of volatile species during phase separation is an important factor to induce diverse mineralization. In contrast, carbonate mineralization is attributed to the significant mixing of vapor‐rich hydrothermal fluid and seawater. A submarine hydrothermal system within a back‐arc basin in the continental margin may be considered as developed in a geologic setting favorable to a diverse range of mineralization, where relatively shallow water depth induces sub‐seafloor phase separation of hydrothermal fluid, and sediment accumulation could enhance migration of the vapor‐rich hydrothermal fluid.     

Trans-boundary and in-country transport of air pollutants observed in Kobe,Japan by high frequent filter pack sampling method

The seasonal intensive sampling of gases and particulate matter in ambient air was conducted at the site established in urban area of Japan to study the seasonal difference of the temporal variation of gases and particulate matter concentrations in urban atmosphere as well as to illustrate the different transport regimes that impacts air pollutants. The sample was collected by the four-stage filter-pack method with 6-h interval for one week in four seasons (spring, summer, autumn and winter). The trans-boundary transport of air pollutants with high concentration was characteristically observed in the spring sampling. On the other hand, we could successfully detect the in-country transports of air pollutants in the summer sampling. Four-season’s intensive survey considered, we could show the characteristic transport of air pollutants to provide the episodic high concentration for ambient air in the urban area of Japan, and successfully illustrate the seasonal-dependent transport regimes to impact on air pollutants.     

High-temperature thermal expansion and elasticity of calcium-rich garnets

We present new high temperature elasticity data on two grossular garnet specimens. One specimen is single-crystal, of nearly endmember grossular, the other is polycrystalline with about 22% molar andradite. Our data extend the high temperature regime for which any garnet elasticity data are available from 1000 to 1350 K and the compositional range of temperature data to near endmember grossular. We also present new data on the thermal expansivity of calcium-rich garnet. We find virtually no discernable differences in the temperatureT derivatives at ambient conditions of the isotropic bulkK _S and shearμ moduli when comparing our results between these two specimens. These calcium-rich garnets have the lowest values of ¦(?K _S /?T) _P ¦ = (1.47,1.49) x 10^-2GPa/K, and among the highest values of ¦(?μ/?T) _P ¦ = 1.25 x 10^-2GPa/K, when compared with other garnets. Small, but measurable, nonlinear temperature dependences of most of the elastic moduli are observed. Several dimensionless parameters are computed with the new data and used to illustrate the effects of different assumptions on elastic equations of state extra-polated to high temperatures. We discuss how dimensionless parameters and other systematic considerations can be useful in estimating the temperature dependence of some properties of garnet phases for which temperature data are not yet available. While we believe it is premature to quantitatively predict the temperature variation ofK _S andμ for majorite garnets, our results have bearing on the amount of diopside required to explain the shear velocity gradients in Earth's transition zone.     

Acetylene reducing activity at a tropical seagrass bed in Papua New Guinea

Acetylene reduction activity at a tropical seagrass bed in Papua New Guinea was studied. Blades of every species of seagrass studied (Enhalus acoroides, Thalassia hemprichii, Halodule uninervis, Syringodium isoetifolium) at the bed showed active acetylene reduction in the rage of 0.025–0.050 mol cm^–2d^–1. It is suggested that epiphytic blue-green algae would be responsible for active acetylene reduction. Acetylene reducing activity was observed also at rhizosphere of seagrasses, microbial communities on the detritus and periphyton on snail shells. It is estimated that total nitrogen fixed at the seagrass bed will be equivalent to 6.7% of that required for the growth of seagrasses.     

Spatial and temporal variations in free polyamine distributions in Uranouchi Inlet, Japan

Polyamines are an essential component of living organisms that influence normal cell growth and development. Despite the possible importance of polyamines for marine microbial ecology, concentrations of polyamines in seawater are not well known.Using HPLC analysis with a cation exchange column and OPA reagent, we determined polyamine concentrations in seawater without carrying out desalting, concentration or derivatization steps prior to chromatography.In seawater collected from Uranouchi Inlet, putrescine and spermidine were the predominant polyamines, ranging from undetectable (N.D.) to 4.4 nM and N.D. to 2.8 nM, respectively. Though other polyamines were detected, the frequency of detection was much lower than that of putrescine and spermidine; concentrations ranged from N.D. to 0.9 nM for cadaverine, and N.D. to 3.2 nM for norspermidine. Norspermine and spermine were detected in only a few samples; their concentrations varied from N.D. to 3.2 nM and N.D. to 0.5 nM, respectively. These concentrations were higher in the summer.