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.     

Thermal anomalies associated with shallow gas hydrates in the K-2 mud volcano, Lake Baikal

Thermal measurements and hydrate mapping in the vicinity of the K-2 mud volcano in Lake Baikal have revealed a particular type of association of thermal anomalies (29–121?mW?m^–2) near hydrate-forming layers. Detailed coring within K-2 showed that hydrates are restricted to two distinct zones at sub-bottom depths exceeding 70–300?cm. Temperature data from stations with hydrate recovery and degassing features all display low thermal gradients. Otherwise, the thermal gradients within the mud volcano are generally increased. These findings imply a more complicated thermal regime than often assumed for mud volcanoes, with important roles for both fluids and hydrates. The coexistence of neighbouring low and high thermal anomalies is interpreted to result from discharging and recharging fluid activity, rather than hydrate thermodynamics. It is suggested that hydrates play a key role in controlling the fluid circulation pattern at an early stage. At a later stage, the inflow of undersaturated lake water would favour the dissolution of structure I hydrates and the formation of structure II hydrates, the latter having been observed on top of structure I hydrates in the K-2 mud volcano.     

Observation of Sea-Ice Thickness Using ENVISAT Data From LÜtzow-Holm Bay, East Antarctica

To investigate the suitability of synthetic aperture radar (SAR) polarization data to estimate the sea-ice thickness in early summer in Lutzow-Holm Bay, Antarctica, we compared in situ ice thicknesses with the corresponding backscattering co-efficient for each polarization and the VV-to-HH backscattering ratio. The VV-to-HH backscattering ratio was derived from data acquired by ENVISAT Advanced SAR (ASAR). This ratio is related to the near-surface dielectric constant of the sea ice, which is, in turn, related to the developing process of ice and, thus, its thickness via changes in the near-surface sea-ice salinity. The sea ice encountered in the study area is close first-year pack ice and fast ice. For these old and relatively rough sea-ice types, the VV-to-HH backscattering ratio can be expected to depend on salinity-driven changes in the near-surface dielectric constant rather than changes of the surface roughness. We applied the empirical relationships between the ice thickness and the VV-to-HH backscattering ratio with the linear and logarithm fits to ASAR data. The linear fit gave the reliable result, with an rms error being 0.08 m and a correlation coefficient being 0.91, when compared to in situ fast-ice thickness.     

Isotope systematics of Li, Sr, Nd, and volatiles in Indian Ocean MORBs of the Rodrigues Triple Junction: Constraints on the origin of the DUPAL anomaly

The DUPAL anomaly, a radiogenic isotope anomaly discovered in the Indian Ocean mantle, has been interpreted as due to a large-scale mantle heterogeneity. To provide new constraints on the DUPAL origin, we analyzed isotope ratios of Li, Sr, and Nd in fresh N-MORB glasses recovered from the Rodrigues Triple Junction in the Indian Ocean, and from the North Atlantic. The Li isotopic compositions of the Indian Ocean DUPAL N-MORBs were comparable to those of the North Atlantic non-DUPAL N-MORBs. The source of the DUPAL signature in Indian Ocean MORBs and the E-MORB-type enriched mantle source have quite different Li isotopic compositions. The ¹⁴³Nd/¹⁴⁴Nd values of both sources are significantly lower than those of the North Atlantic N-MORBs. The δ⁷Li values of most oceanic island basalts with similar low ¹⁴³Nd/¹⁴⁴Nd signatures are also higher than those of the North Atlantic N-MORBs, except for several Koolau lavas. The Li isotope results support the recent proposal that significant amounts of recycled lower continental crust might produce the radiogenic isotope signatures of the Indian Ocean DUPAL source.     

Deserpentinization and high-pressure(eclogite-facies) metamorphic features in the Eoarchean ultramafic body from Isua,Greenland

Discontinuous chains of ultramafic rock bodies form part of the 3800–3700 Ma Isua Supracrustal Belt(ISB),hosted in the Itsaq Gneiss Complex of southwestern Greenland.These bodies are among the world’s oldest outcrops of ultramafic rocks and hence an invaluable geologic record.Ultramafic rocks from Lens B in the northwestern limb of ISB show characteristics of several stages of serpentinization and deserpentinization forming prograde and retrograde mineral assemblages.Ti-rich humite-group minerals such as titanian chondrodite(Ti-Chn)and titanian clinohumite(Ti-Chu)often occur as accessory phases in the metamorphosed ultramafic rocks.The Ti-rich humite minerals are associated with metamorphic olivine.The host olivine is highly forsteritic(Fo96-98)with variable Mn O and Ni O contents.The concentrations of the rare-earth elements(REE)and high-field strength elements(HFSE)of the metamorphic olivine are higher than typical mantle olivine.The textural and chemical characteristics of the olivine indicate metamorphic origin as a result of deserpentinization of a serpentinized ultramafic protolith rather than primary assemblage reflecting mantle residues from high-degrees of partial melting.The close association of olivine,antigorite and intergrown Ti-Chn and Ti-Chu suggests pressure condition between$1.3–2.6 GPa within the antigorite stability field(<700°C).The overall petrological and geochemical features of Lens B ultramafic body within the Eoarchean ISB indicate that these are allochthonous ultramafic rocks that recorded serpentine dehydration at relatively lower temperature and reached eclogite facies condition during their complex metamorphic history similar to exhumed UHP ultramafic rocks in modern subduction zone channels.     

Lithium and strontium isotopic systematics in playas in Nevada,USA: constraints on the origin of lithium

Lithium-rich brine in playas is a major raw material for lithium production. Recently, lithium isotopic ratios (δ⁷Li) have been identified as a tool for investigating water–rock interactions. Thus, to constrain the origin of lithium in playas by the use of its isotopes, we conducted leaching experiments on various lacustrine sediment and evaporite deposit samples collected from playas in Nevada, USA. We determined lithium and strontium isotopic ratios and contents and trace element contents of the leachate, estimated the initial δ⁷Li values in the water flowing into the playas, and examined the origin of lithium in playas by comparison with δ⁷Li values of the possible sources. In samples from the playas, δ⁷Li values show some variation, reflecting differences both in isotopic fractionation during mineral formation and in initial δ⁷Li value in water flowing into each playa. However, all δ⁷Li values in this study are much lower than those in river water and groundwater samples from around the world, but they are close to those of volcanic rocks. Considering the temperature dependence of lithium isotopic fractionation between solid and fluid, these results indicate that the lithium concentrated in playas in Nevada was supplied mainly through high-temperature water–rock interaction associated with local hydrothermal activity and not directly by low-temperature weathering of surface materials. This study, which is the first to report lithium isotopic compositions in playas, demonstrates that δ⁷Li may be a useful tracer for determining the origin of lithium and evaluating its accumulation processes in playas.     

Precise Determination of the Coordinate Systems for the Yohkoh Telescopes and the Application of a Transit of Mercury

The Yohkoh solar X-ray observatory carries two telescopes that require coalignment at a level better than the minimum pixel size of 2_45. This coalignment is needed both internally within Yohkoh and for many scientific applications involving data from ground-based radio and optical observatories. We describe the methods successfully developed for this purpose and now incorporated in the Yohkoh software. Soft X-ray observations of the 1993 transit of Mercury across the solar disk provided key information for the calibration of the coalignment procedures.     

Laser-Dye Imaging of the pH Field in a Laboratory Experiment

We established a precise DeLIF (Dual Emission Laser Light Fluorescence) system for the instant measurement of the pH field in laboratory experiments. This method is very important in studies of the biological impacts of CO₂ sequestration, i.e., effects of pH on organisms. The technique is demonstrated by applying it to the pH measurement around a liquid CO₂ droplet, which has a large gradient of CO₂ concentration near its interface, the concentration value on the boundary being known as the solubility of CO₂. In the Laser Induced Fluorescence (LIF) method using quinine and an ultraviolet laser light source, the relatively unstable pulse of the laser source decreased the measurement reliability. We therefore investigated many kinds of fluorescent dye and demonstrated the DeLIF measurement, identifying a process for cancelling fluctuations of laser light intensity. Quinine and sulforhodamine were used as fluorescence dyes. The molar absorption coefficient and emission intensity of quinine depend on the pH of aqueous solutions, while those of sulforhodamine are not as much affected by pH. The ratio of these fluorescence intensities represents pH at each point of the image. As a result, the pH field was successfully measured with an uncertainty of only approximately ±0.005, for 3.0 < pH. This revised version was published online in July 2006 with corrections to the Cover Date.     

A Eulerian-Eulerian Physical-Biological Impact Model of Zooplankton Injury Due to CO<Subscript>2</Subscript> Ocean Sequestration

To study the biological impacts of CO₂ ocean sequestration on floating marine organisms, a full Eulerian-Eulerian scheme model has been developed in a large-eddy simulation (LES) version using one-way coupling of the equations of seawater flow to the transport equations of the bio-scalar variables. Special attention was paid to deriving the transport equation, involving non-conservative scalars to describe the degree of injury to floating organisms due to the change in the pH environment resulting from CO₂ dissolution. The source terms of the transport equations of bio-scalar variables are based on experimental data on zooplankton activities affected by lower pH seawater, allowing construction of empirical sub-models of three kinds of floating marine organisms: Gaidius variabilis, Paraeuchaeta Birostrata, and Multi-organisms. An example is given to show the applicability of the model to the assessment of the biological impact of CO₂ sequestration in the ocean. Given an initial CO₂ droplet diameter of 8.0 mm and an injection rate of 1.0 kg/sec, the model simulation predicts that the zooplanktons lose approximately 90% of their activity when the lowest pH inside the plume decreases from 7.57 to 5.61. These injured zooplanktons then recovered gradually to their normal state within two hours due to dilution of the plume. This revised version was published online in July 2006 with corrections to the Cover Date.     

Occurrence of PSP-producing dinoflagellate Alexandrium tamiyavanichii in Bingo-Nada, the central coastal water of the Seto Inland Sea, Hiroshima Prefecture, Japan

During surveillance of the distribution of the paralytic shellfish poison (PSP)-producing dinoflagellate in 2003, 2004 and 2005 along the coastlines of the Seto Inland Sea, Hiroshima Prefecture, Japan, some species of toxic phytoplankton were isolated from the eastern coasts, Bingo-Nada, the central regions of the Seto Inland Sea. It was rather unexpectedly revealed from the basis of the morphological characteristics that they were unambiguously identified as Alexandrium tamiyavanichii and Alexandrium catenella. Two strains (ATY041106, ATY051018) of A. tamiyavanichii showed a specific toxicity of 38.7 x 10(-6) and 111.5 x 10(-6)MU/cell, respectively. These values seemed to be several times or much higher than that of A. catenella (AC030816, AC040614), having a specific toxicity of 4.5 x 10(-6) and 4.1 x 10(-6)MU/cell, respectively, isolated in the same area. From the results of HPLC-furuorometric analysis, it revealed that the toxins in ATY041106 exist almost exclusively as beta-epimers (C2, GTX3, GTX4), which accounted for 72.7 mol%. The toxin profiles of this strain are featured by the presence of a large amount of GTX3 (59.1 mol%) and a small amount (20.6%) of C1 and 2 in comparison with the PSP compositions of A. tamarense, which is isolated as the main responsible species in Hiroshima Bay, a western part of coastal sea in Hiroshima Prefecture. On the other hand, it revealed that the toxin profiles of two strains (AC030816, AC040614) of A. catenella exist almost exclusively as beta-epimers (C2, GTX3, GTX4), which accounted for 81.8 and 56.5 mol%, as the same manner. The toxin profiles of these two strains are featured by the presence of a large amount of C2 (80.5 and 46.3 mol%) in comparison with the PSP compositions of A. tamiyavanichii. To our knowledge, this is the first record to show the distribution and harmful influence of A. tamiyavanichii and A. catenella in Bingo-Nada in Hiroshima Prefecture. Though contamination of bivalves with these PSP-producing planktons in this area has not occurred yet so far, attention should be paid to this species as well as the other causative dinoflagellate from the stand point of public health and food hygiene.