Formation experiments of CO2 hydrate chimney in a pressure cell

Experimental investigations were conducted to understand the formation process of CO_2 hydrate the chimney structure by using a gas bubble emission technique in water within a pressure cell. The detailed process was video-recorded and analyzed to study the initiation and growth behavior of hydrate chimney while the cell pressure was increased and gas supply rate decreased gradually with time. In the initial stage of chimney growth, a hydrate crystal started to form in a cup shape at the gas nozzle and ascended together with gas bubbles due to mechanical weakness of the hydrate/nozzle contact. Growth of hydrate chimney occurred with supercooling of 3K(overpressure of 0.60MPa) or more, and continued until the top end was closed completely by hydrate

Numerical modelling of sublimation on snow and comparison with field measurements

Various field observations of surface-hoar formation were carried out with measurements of vapor sublimation rate and meteorological conditions from 1994 to 1996 in a mountainous area of northern Hokkaido,Japan. The sublimation rate seemed to increase with wind speed when the relative humidity was high, whereas the sublimation rate changed from positive to negative as the wind speed increased when the relative humidity was low (60–70%RH). These results were explained with a numerical model (called the Simple model) for the heat balance at the snow surface; the results of the model showed that there is a specific wind speed which maximizes the sublimation rate when the relative humidity is low, and indicated that the sublimation rate becomes large under humid conditions (>90%RH) and if wind speeds are increasing in the range 0.5–3.5 m s–1. The heat balance at the snow surface reproduced by another snow model, Crocus, agreed well with the observation results. However, Crocus overestimated the sublimation rate by about 1.3 × 10–6 kg m–2 s–1 when surface hoar formed, and underestimated snow surface temperature by several degrees.journal articl

Crystallization of authigenic carbonates in mud volcanoes at Lake Baikal

This paper presents data on authigenic siderite first found in surface sediments from mud volcanoes in the Central (K-2) and Southern (Malen’kii) basins of Lake Baikal. Ca is the predominant cation, which substitutes Fe in the crystalline lattice of siderite. The enrichment of the carbonates in the 13C isotope (from +3.3 to +6.8‰ for the Malen’kii volcano and from +17.7 to +21.9‰ for K-2) results from the crystallization of the carbonates during methane generation via the bacterial destruction of organic matter (acetate). The overall depletion of the carbonates in 18O is mainly inherited from the isotopic composition of Baikal water

Temperature effects on the C–H symmetric stretching vibrational frequencies of guest hydrocarbon molecules in 512, 51262 and 51264 cages of sI and sII clathrate hydrates

C–H symmetric stretching vibrational frequencies of CH4, C2H4 and C2H6 molecules encapsulated in 512, 51262 and 51264 cages of structures I (sI) and II (sII) clathrate hydrates measured by Raman spectroscopy in the temperature range of 93–183 K was analysed. The slopes of the symmetric stretch vibrational frequencies under changing temperatures (Δv/ΔT) for CH4, C2H4 and C2H6 molecules encapsulated in sII 51264 cages were smaller than those for molecules in sI 51262 cages, although sI 51262 cages are smaller than sII 51264 cages. We compared the results of Δv/ΔT in this study with the geometrical properties of each host water cage, and these comparisons suggest that the geometry of host water cages affects Δv/ΔT.journal articl

Effect of wind on surface hoar growth on snow

Field observations of surface hoax formation were carried out with the measurementso f water vapor condensationr ate, snows urfacet emperature, air temperature, humidity, wind speed, and net radiation. Large surface hoar crystals wereo bservetdo formu ndert he breezyw ind,I to 2 m s- i, at 0.1m high. The condensationra te increasedli nearly with the producto f the vapor pressureg radient and the wind speed. The bulk transferc oefficienot f water vapor Ce was roughly constant when the surface hoar crystals were small, whereas it showed some increase as the hoarc rystalsg rewt o severaml illimeterisn height.A possiblcea useo f this increase in Ce is that the developed surface hoar crystals modify the aerodynamic roughnessa nd consequentliyn creaseth e turbulentt ransfero f water vapor.journal articl

Effect of temperature and large guest molecules on the C–H symmetric stretching vibrational frequencies of methane in structure H and I clathrate hydrates

Large molecules such as 2-methylbutane (C5H12) or 2,2-dimethylbutane (C6H14) form structure H (sH) hydrates with methane (CH4) as a help gas. In this study, the Raman spectra of the C–H symmetric stretch region of CH4 enclathrated within various sH hydrates and structure I CH4 hydrates were analyzed in the temperature range 137.7–205.4 K. Thermal expansions of these sH hydrate samples were also measured using powder X-ray diffraction. Symmetric stretch vibrational frequencies of CH4 in host– water cages increased because of varying temperature, and the sizes of the host–water cages also increased; variation of CH4 in small cages was less than in larger cages. Comparing the variations of the C–H symmetric stretching frequencies of CH4 in gas hydrates with varying pressure and temperature, we suggest that the observed trend is caused by thermal vibrations of the CH4 molecule in water cages.journal articl

Effects of snow physical parameters on shortwave broadband albedos

Snow pit work of several-day intervals was performed simultaneously with radiation budget observations during two winters in eastern Hokkaido, Japan. From these data we investigated the effects of elapsed time after snowfall (snow aging), air temperature, snow surface temperature, snow grain size, and snow impurities on the visible and the near infrared albedos for improving the snow albedo scheme in the land surface process from an empirical model to a physically based model. The dependence of albedos on elapsed time after snowfall could be clearly classified by dividing the snow-covered period into a dry snow season and a wet snow season rather than by snow surface temperature. The albedo reduction by snow aging statistically depends on the snow surface temperature, which is often used to predict the snow albedo in the empirical model of land surface process. However, the albedo reduction rate was very scattered for snow surface temperatures above 10 C. This is because the snow albedo reduction essentially depends on the snow grain size and the concentration of snow impurities. Using the radiative transfer model for the atmosphere-snow system, the effects of these snow physical parameters on broadband albedos are calculated and compared with the observed ones. The measured broadband albedos fell close to the range of theoretically calculated ones as functions of these snow physical parameters. In particular, the measured near infrared albedo agreed well with the theoretically calculated ones both for the dependence of snowgrain size and snow impurities but not as well for the visible albedo in detail. In the near infrared region the light absorption by ice is strong, and thus the snow albedo contains the information of snow physical parameters near the surface where these parameters are measured. In contrast, the visible albedo contains the snow information in the deeper layer because the ice is relatively transparent in the visible region. This suggests the necessity of the multiple-snow-layer model for the visible region in the physically based snow albedo model.journal articl

Mass fractionation of noble gases in synthetic methane hydrate : implications for naturally occurring gas hydrate dissociation

This paper is not subject to U.S. copyright. The definitive version was published in Chemical Geology 339 (2013): 242-250, doi:10.1016/j.chemgeo.2012.09.033.As a consequence of contemporary or longer term (since 15 ka) climate warming, gas hydrates in some settings may presently be dissociating and releasing methane and other gases to the ocean–atmosphere system. A key challenge in assessing the impact of dissociating gas hydrates on global atmospheric methane is the lack of a technique able to distinguish between methane recently released from gas hydrates and methane emitted from leaky thermogenic reservoirs, shallow sediments (some newly thawed), coal beds, and other sources. Carbon and deuterium stable isotopic fractionation during methane formation provides a first-order constraint on the processes (microbial or thermogenic) of methane generation. However, because gas hydrate formation and dissociation do not cause significant isotopic fractionation, a stable isotope-based hydrate-source determination is not possible. Here, we investigate patterns of mass-dependent noble gas fractionation within the gas hydrate lattice to fingerprint methane released from gas hydrates. Starting with synthetic gas hydrate formed under laboratory conditions, we document complex noble gas fractionation patterns in the gases liberated during dissociation and explore the effects of aging and storage (e.g., in liquid nitrogen), as well as sampling and preservation procedures. The laboratory results confirm a unique noble gas fractionation pattern for gas hydrates, one that shows promise in evaluating modern natural gas seeps for a signature associated with gas hydrate dissociation.Partial support for this research was provided by Interagency Agreements DE-FE0002911 and DE-NT0006147 between the U.S. Geological Survey Gas Hydrates Project and the U.S. Department of Energy's Methane Hydrates Research and Development Program

Возраст грязевой брекчии грязев ых вулканов Академического хреб та озера Байка

Lake Baikal is the only freshwater reservoir on Earth with gas-hydrate accumulations in its bottom sediments, partly due to the activity of mud volcanoes. This paper describes a group of mud volcanoes recently discovered on the slope of the Academician Ridge between the northern and central Lake Baikal basins. Our analysis of diatom skeletons in the mud breccia sampled from the study area shows a high abundance of Cyclotella iris et var. These extinct species were also discovered in a core sample from BDP-98 borehole. Based on the biostratigraphic and seis-mostratigraphic correlations, the age of the mud breccia in the studied mud volcanoes ranges from the Late Miocene to the Early Pliocene (4.6 to 5.6 Ma). The correlations suggest that the material originated from a depth of less than 310 m below the lake bottom

Calorimetric and Powder X-ray Diffraction Studies on Dissociation of Methane Hydrate in Porous Media

Dissociation processes of synthetic methane hydrate with glass beads were reported by using a calorimetric system and powder X-ray diffraction. Methane hydrate formed with coarse glass beads (size: 30.8, 56.3, and 100.4 μm) rather quickly dissociated at 150-200 K, whereas about 40 % of that with fine glass beads (size: 0.4 μm) still survived at 200 K. These results are contrasting with the size effect of methane hydrate particles reported by Takeya et al. (2005) that larger particles can retain themselves than smaller particles.conference pape