Raman spectra of methane hydrate up to 86 GPa

High-pressure Raman studies of methane hydrate were performed using a diamond anvil cell in the pressure range of 0.1–86 GPa at room temperature. Raman spectra of the methane molecules revealed that new softened intramolecular vibration mode of ν ₁ appeared at 17 GPa and that the splitting of vibration mode of ν ₃ occurred at 15 GPa. The appearance of these two modes indicates that an intermolecular attractive interaction increases between the methane molecules and the host water molecules and between the neighboring methane molecules. These interactions might result in the exceptional stability of a high-pressure structure, a filled ice Ih structure (FIIhS) for methane hydrate, up to 40 GPa. At 40 GPa, a clear change in the slope of the Raman shift versus pressure occurred, and above 40 GPa the Raman shift of the vibration modes increased monotonously up to 86 GPa. A previous XRD study showed that the FIIhS transformed into another new high-pressure structure at 40 GPa. The change in the Raman spectra at 40 GPa may be induced by the transition of the structure.     

Mesoscale structures of two types of cold-air outbreaks over the East China Sea and the effect of coastal sea surface temperature

Two types of cold-air outbreaks over the Yellow and East China Seas are investigated using a regional mesoscale model. Distinct patterns of surface turbulent heat fluxes and precipitation are identified between the two cases. The sea surface heat flux and frictional velocity are strongly influenced by mesoscale differences between high- and low-resolution datasets of sea surface temperature (SST). The influence of the SST difference on atmospheric water is spread to the downstream area of the outbreak with the phase transition of water. The air mass transformation around 800?hPa over the Kuroshio is partly influenced by the upstream SST difference. In particular, the SST difference near the mouth of the Yanzi River strongly modifies the air mass around Taiwan. Thus, in addition to the Kuroshio front, the mesoscale Chinese coastal SST structure is also important in the air mass transformation over the East China Sea.     

Ore mineralogy and sulfur isotope study of the massive sulfide deposit of Filon Norte,Tharsis Mine,Spain

The volcanogenic massive sulfide deposit of Filon Norte at Tharsis is hosted by carbonaceous black slate and connected only partly with stockwork veins. The massive ores are usually composed of fine-grained pyrite with subordinate amounts of sphalerite, chalcopyrite, galena and arsenopyrite. Monoclinic pyrrhotite sometimes occurs in massive pyritic ores in the apparently middle and upper horizons of the orebody, and siderite-rich ores are interstratified with compact pyritic ores in the apparently lower horizons. From the occurrence of monoclinic pyrrhotite, together with the FeS contents of sphalerite mostly ranging from 11 to 16 mol %, it is inferred that the sulfide minerals of the massive orebody were precipitated in euxinic muds on the sea-floor at temperatures below 250°C. The negatively shifted, highly variable ³⁴S values of the massive ores and their close similarity to those of the underlying black slates strongly suggest that the sulfide sulfur of the massive orebody and the slates is cognate and biogenic.     

Interstellar cyanomethane

We have made an observational study of the newly identified cyanomethane radical CH2CN and the possibly related species CH3CN with the goals of (1) elucidating the possible role of reactions of the type CnHm(+) + N in astrochemistry, and (2) providing a possible test of Bates's models of dissociative electron recombination. We find a remarkably different abundance ratio CH2CN/CH3CN in TMC-1 and Sgr B2, which we deduce is a result of the large difference in temperature of these objects. Studies of CH2CN and CH3CN in other sources, including two new detections of CH2CN, support this conclusion and are consistent with a monotonic increase in the CH2CN/CH3CN ratio with decreasing temperature over the range 10-120 K. This behavior may be explained by the destruction of CH2CN by reaction with O. If this reaction does not proceed, then CH2CN and CH3CN are concluded to form via different chemical pathways. Thus, they do not provide a test of Bates's conjectures (they do not both form from CH3CNH+). CH2CN is then likely to form via C2H4(+) + N --> CH2CNH+, thus demonstrating the viability of this important reaction in astrochemistry. The T dependence of the CH2CN/CH3CN ratio would then reflect the increasing rate of the C2H4(+) + N reaction with decreasing temperature.     

Laboratory detection of a new interstellar free radical CH2CN(2B1)

An asymmetric-top free radical CH2CN, which as a 2B1 ground state, was detected for the first time by laboratory microwave spectroscopy. The radical was produced in a free-space absorption cell by a DC glow discharge in pure CH3CN gas. About 60 fine-structure components were observed for the N = 11-10 to 14-13 a-type rotational transitions in the frequency region of 220-260 GHz, and many hyperfine resolved components for the N = 4-3 and 5-4 transitions in the 80 and 100 GHz regions, respectively. The molecular constants, including the rotational constants, centrifugal distortion constants, and spin-rotation coupling constants with centrifugal distortion correction terms were determined from the fine-structure resolved transitions, and the hyperfine coupling constants due to the hydrogen and nitrogen nuclei were obtained from the low-N transitions. As a result we assigned U100602 and U80484 from Sgr B2, and U40240 and U20120 from TMC-1, to the N = 5-4, 4-3, 2-1, and 1-0 transitions with K-1 = 0 of the CH2CN radical.     

Ca isotopic compositions of dolomite, phosphorite and the oldest animal embryo fossils from the Neoproterozoic in Weng'an, South China

Deciphering the drastic changes of surface environment and the emergence of animals after the Neoproterozoic Snowball Earth event are important for understanding the changes of surface environment and its influence on the evolution of life through geologic time. Especially, the emergence of two types of Metazoan animals such as animal embryo fossils, cnidarians or sponges, and Ediacaran fauna in the late Neoproterozoic was one of the critical turning points in the biological evolution.Calcium is one of the essential elements for the growth of most animals. In this study, in order to evaluate the Ca cycles in the Neoproterozoic, we have measured Ca isotopic ratios (⁴⁴Ca/⁴²Ca and ⁴³Ca/⁴²Ca) for phosphorite, dolostone and phosphatic animal embryo fossils with a multiple collector, inductively coupled plasma-mass spectrometer (MC-ICP-MS). The resulting ⁴⁴Ca/⁴²Ca ratio defined by the relative deviation from the ratio of NIST SRM915a (δ^44/42Ca_NIST915) for phosphorite and dolostone ranges from 0.83 to 0.95‰, demonstrating that the fractionation between phosphorite/dolostone and seawater was very small. This evidence indicates that at the emergence of the Weng'an biota seawater was deficient in Ca probably due to mass deposition of phosphorite/dolostone and to the beginning of Ca-biomineralization.Three phosphatic animal embryo fossils have lower δ^44/42Ca values than the phosphorite and dolomite, implying that the precursor of the phosphatic embryo fossils was able to fractionate Ca isotopes through Ca-biomineralization, consistent with marine gastropods.     

Occurrence of phosphatic microfossils in an Ediacaran–Cambrian mid-oceanic paleo-atoll limestone of southern Siberia

New phosphatic microfossils were recently discovered in an Ediacaran–Cambrian mid-oceanic paleo-atoll limestone in the southern Gorny Altai Mountains in southern Siberia. Microfossils with calcium phosphate shells are abundant in the limestone that occurs as an exotic block within a Cambrian accretionary complex in the Kurai area. SEM observations confirm that the calcium phosphatic shells are ellipsoidal and equal-sized, about 200–300 μm in diameter. Shell walls are about 1 μm thick. As the absence of external and internal structures hinders a detailed comparison/identification, these microfossils are tentatively treated here as paleontological problematica. EPMA-analysis confirmed the concentration of elements P and Ca in microfossil shells and the absence in the matrix, suggesting the primary phosphatic composition of the shells. Because phosphatic microfossils are generally scarce in the Ediacaran but abundant from the Lower Cambrian, in particular within pre-trilobitic SSF assemblages, the phosphatic fossil-bearing limestone in the Kurai area possibly belongs to the Lower Cambrian. The present find proves that mid-oceanic paleo-seamounts as well as continental shelf domains had already been inhabited by diverse metazoans in the Ediacaran–Cambrian transitional interval.     

The development of Fe-nodules surrounding biological material mediated by microorganisms

Takashikozo is a phenomenon of Quaternary sediments in Japan. They are cylindrical Fe-oxyhydroxide nodules that form as plaques round plant roots, where Fe is preferentially concentrated to develop a solid wall. Structural features suggest that after the roots have decayed, the central space where the roots were situated acts as a flow path for oxidized water. Analysis of microbial 16S rDNA extracted from the nodules identified iron-oxidizing bacteria encrusted round the roots where they are the likely initiators of nodule formation. Direct microscopic observation revealed an accumulation of Fe-oxyhydroxides that fill the pore spaces and is also likely to be linked with the encrusting microbial colonies. Geological history and nanofossil evidence suggest that these Fe-nodules may have been buried at a depth of up to several tens of meters for at least 10⁵ years in reducing Quaternary sediments. Thus Fe-oxyhydroxide nodules that have formed in a geological environment at the interfaces between water and rock by microbial mediation can persist under reducing conditions. If this is the case, the phenomenon is significant as an analogue of post-closure conditions in radioactive waste repositories, since it could influence nuclide migration.     

Dynamics of elastically moored floating objects

The two-dimensional problem of wave transformation by, and motions of, moored floating objects is solved numerically as a boundary value problem by direct use of Green's identity formula for a potential function. The cross-sectional shape of the floating object, the bottom configuration and the mooring arrangements may be all arbitrary. For a given incident wave, the three modes of body motion, the wave system and mooring forces are all solved at the same time. A laboratory experiment is conducted to verify the theory. Generally good agreements between the theory and experiments are obtained as long as the viscous damping due to flow separation is small. A numerical experiment indicates that a conventional sluck mooring is to worsen the wave attenuation by a floating breakwater and that a properly arranged elastic mooring can considerably improve the wave attenuation by a floating breakwater.