Interpretation of the relationship between benthic fauna, geologic distributions, and methane seeps at Southern Hydrate Ridge, Oregon continental margin

Senior thesis written for Oceanography 445

Analysis of Parameter Values in the van der Waals and Platteeuw Theory for Methane Hydrates Using Monte Carlo Molecular Simulations

The van der Waals and Platteuw (vdVVP) theory has been successfully used to model the thermodynamics of gas hydrates. However, earlier studies have shown that this could be due to the presence of a large number of adjustable parameters whose values are obtained through regression with experimental data. To test this assertion, we carry out a systematic and rigorous study of the performance of various models of vdWP theory that have been proposed over the years. The hydrate phase equilibrium data used for this study is obtained from Monte Carlo molecular simulations of methane hydrates. The parameters of the vdWP theory are regressed from this equilibrium data and compared with their true values obtained directly from simulations. This comparison reveals that (i) methane-water interactions beyond the first cage and methane-methane interactions make a significant contribution to the partition function and thus cannot be neglected, (ii) the rigorous Monte Carlo integration should be used to evaluate the Langmuir constant instead of the spherical smoothed cell approximation, (iii) the parameter values describing the methane-water interactions cannot be correctly regressed from the equilibrium data using the vdVVP theory in its present form, (iv) the regressed empty hydrate property values closely match their true values irrespective of the level of rigor in the theory, and (v) the flexibility of the water lattice forming the hydrate phase needs to be incorporated in the vdWP theory. Since methane is among the simplest of hydrate forming molecules, the conclusions from this study should also hold true for more complicated hydrate guest molecules.

Study on the Mechanical Properties of the Tetrahydrofuran Hydrate Deposit

Pure tetrahydrofuran hydrate and tetrahydrofuran hydrate deposits with different materials as the skeleton are synthesized in our laboratory. A series of experiments are carried out to study the mechanical properties. The stress-strain curve, strength of pure tetrahydrofuran hydrate and hydrate deposit are obtained. Some phenomenon is explained.

Gas-bearing fluid influx sub-system for gas hydrate geological system in Shenhu Area, Northern South China Sea

Based on the comprehensive interpretation and study of the Neogene fracture system and diapiric structure, it can be concluded that the diapiric structures, high-angle fractures and vertical fissure system are the main gas-bearing fluid influx sub-system for gas hydrate geological system in Shenhu Area, northern South China Sea. The Neogene fractures widely developed in the study area may be classed into two groups: NW (NNW)-trending and NE (NNE)-trending. The first group was active in the Late Miocene, while the second one was active since the Pliocene. The NE (NNE)-trending fractures were characterized by lower activity strength and larger scale, and cut through the sediment layers deposited since the Pliocene. Within the top sediment layers, the high-angle fracture and vertical fissure system was developed. The diapiric structures display various types such as a turtle-back-like arch, weak piercing, gas chimney, and fracture (or crack, fissure). On the seismic profile, some diapiric structures show the vertical chimney pathway whose top is narrow and the bottom is wide, where some ones extend horizontally into pocket or flower-shaped structures and formed the seismic reflection chaotic zones. Within the overlying sediment layers of the diapiric structure, the tree branch, flower-shaped high-angle fractures and vertical fissures were developed and became the pathway and migration system of the gas-bearing fluid influx. In the study area, the diapiric structures indicate a high temperature/over pressure system ever developed. Closely associated and abundant bright-spots show the methane-bearing fluid influx migrated vertically or horizontally through the diapiric structures, high-angle fractures and vertical fissures. In the place where the temperature and pressure conditions were favor for the formation of gas hydrate, the hydrate reservoir deposition sub-system was developed.

In situ hydrate dissociation using microwave heating: Preliminary study

In this work, we investigate the dissociation behavior of natural gas hydrate in a closed system with microwave (MW) heating and hot water heating. The hydrate was formed at temperatures of 1-4 degrees C and pressures of 4.5-5.5 MPa. It was found that the gas hydrate dissociated more rapidly with microwave than with hot water heating. The rate of hydrate dissociation increased with increasing microwave power, and it was a function of microwave power. Furthermore, the temperature of the hydrate increased linearly with time during the microwave radiation.

Clathrate Dissociation Conditions for Methane + Tetra-n-butyl Ammonium Bromide (TBAB) + Water

Hydrate equilibrium data of the CH4 + tetra-n-butyl ammonium bromide (TBAB) + water have been measured by using the isothermal pressure search method for four components of TBAB aqueous solutions. The three-phase equilibrium lines obtained in the present study are shifted to the low-temperature or high-pressure side from that of the stoichiometric TBAB solution. Moreover, methane uptake into semi-clathrates is confirmed by a shift in the clathrate regions when methane is present. The experiments are carried out in the pressure range of (0.5 to 11) MPa and in the temperature range of (281.15 to 295.15) K.

Study on methane hydration process in a semi-continuous stirred tank reactor

The methane hydration process is investigated in a semi-continuous stirred tank reactor. Liquid temperatures and reaction rates without stirrer are compared with those occurring with stirrer, while at the same time better stirring conditions of the methane hydration process are given by the experiments. Some basic data of fluid mechanics, for example, stirring Reynolds number, Froucle number and stirrer power, are calculated during the methane hydration process, which can be applied to evaluate stirrer capacity and provide some basic data for a scaled up reactor. Based on experiment and calculations in this work, some conclusions are drawn. First, the stirrer has great influence on the methane hydration process. Batch stirring is helpful to improve the mass transfer and heat transfer performances of the methane hydration process. Second, induction time can be shortened effectively by use of the stirrer. Third, in this paper, the appropriate stirring velocity and stirring time were 320 rpm and 30 min, respectively, at 5.0 MPa, for which the storage capacity and reaction time were 159.1 V/V and 370 min, respectively. Under the condition of the on-flow state, the initial stirring Reynolds number of the fluid and the stirring power were 12,150 and 0.54 W, respectively. Fourth, some suggestions, for example, the use of another type of stirrer or some baffles, are proposed to accelerate the methane hydration process. Comparing with literature data, higher storage capacity and hydration rate are achieved in this work. Moreover, some fluid mechanics parameters are calculated, which can provide some references to engineering application.

Methane-derived authigenic carbonates from the Ulleung basin sediments, East Sea of Korea

Authigenic carbonates were sampled in methane-enriched piston core sediments collected from gas venting sites on the western continental slope of the Ulleung Basin, East Sea of Korea. Multidisciplinary investigations on these carbonates, including the scanning electronic microscope (SEM) observations and mineralogical-geochemical compositions, were carried out to identify the carbon and oxygen sources and the forming mechanism of these carbonates. The authigenic carbonates from the study area correspond to semi-consolidated, compact concretions or nodules ranging from 2 to 9 cm in size. X-ray diffraction and electron microprobe analyses showed that most of the sampled carbonate concretions were composed of almost purely authigenic high-Mg calcite (10.7-14.3 mol% MgCO3). Characteristically, microbial structures such as filaments and rods, which were probably associated with the authigenic minerals, were abundantly observed within the carbonate matrix. The carbonates were strongly depleted in delta C-13 (-33.85 parts per thousand to -39.53 parts per thousand Peedee Belemnite (PDB)) and were enriched in delta O-18 (5.16-5.60 parts per thousand PDB), indicating that the primary source of carbon is mainly derived from the anaerobic oxidation of methane. Such methane probably originated from the destabilization of the underlying gas hydrates as strongly supporting from the enriched O-18 levels. Furthermore, the strongly depleted delta C-13 values (-60.7 parts per thousand to -61.6 parts per thousand PDB) of the sediment void gases demonstrate that the majority of the gas venting at the Ulleung Basin is microbial methane by CO2 reduction. This study provides another example for the formation mechanism of methane-derived authigenic carbonates associated with gas-hydrate decomposition in gas-seeping pockmark environments. (c) 2009 Elsevier Ltd. All rights reserved.

Genetic model of the hydrate system in the fine grain sediments in the northern continental slope of South China Sea

Gas hydrate samples were obtained firstly in China by drilling on the northern margin of South China Sea (SCS). To understand the formation mechanism of this unique accumulation system, this paper discusses the factors controlling the formation of the system by accurate geophysical interpretation and geological analysis, based on the high precision 2-D and 3-D multichannel seismic data in the drilling area. There are three key factors controlling the accumulation of the gas hydrate system in fine grain sediment: (1) large volume of fluid bearing methane gas Joins the formation of gas hydrate. Active fluid flow in the northern South China Sea makes both thermal gas and/or biogenic gas migrate into shallow strata and form hydrate in the gas hydrate stability zone (GHSZ). The fluid flow includes mud diapir and gas chimney structure. They are commonly characterized by positive topographic relief, acoustic turbidity and push-down, and low reflection intensity on seismic profiles. The gas chimneys can reach to GHSZ, which favors the development of BSRs. It means that the active fluid flow has a close relationship with the formation and accumulation of gas hydrate. (2) The episodic process of fracture plays an important role in the generation of gas hydrate. It may provide the passage along which thermogenic or biogenic gas migrated into gas hydrate stability zone (GHSZ) upward. And it increases the pore space for the growth of hydrate crystal. (3) Submarine landslide induced the anomalous overpressure activity and development of fracture in the GHSZ. The formation model of high concentration gas hydrate in the drilling sea area was proposed on the basis of above analysis.

Characteristics of shallow gas hydrate in Okhotsk Sea

Multidisciplinary field investigations were carried out in Okhotsk Sea by R/V Akademik M.A. Lavrentyev (LV) of the Russian Academy of Sciences (RAS) in May 2006, supported by funding agencies from Korea, Russia, Japan and China. Geophysical data including echo-sounder, bottom profile, side-scan-sonar, and gravity core sample were obtained aimed to understand the characteristics and formation mechanism of shallow gas hydrates. Based on the geophysical data, we found that the methane flare detected by echo-sounder was the evidence of free gas in the sediment, while the dome structure detected by side-scan sonar and bottom profile was the root of gas venting. Gas hydrate retrieved from core on top of the dome structure which was interbedded as thin lamination or lenses with thickness varying from a few millimeters to 3 cm. Gas hydrate content in hydrate-bearing intervals visually amounted to 5%-30% of the sediment volume. This paper argued that gases in the sediment core were not all from gas hydrate decomposition during the gravity core lifting process, free gases must existed in the gas hydrate stability zone, and tectonic structure like dome structure in this paper was free gas central, gas hydrate formed only when gases over-saturated in this gas central, away from these structures, gas hydrate could not form due to low gas concentration.

Bottom simulating reflector and gas seepage in Okinawa Trough: Evidence of gas hydrate in an active back-arc basin

To look for gas hydrate, 22 multi-channel and 3 single-channel seismic lines on the East China Sea (ECS) shelf slope and at the bottom of the Okinawa Trough were examined. It was found that there was indeed bottom simulating reflector (BSR) occurrence, but it is very rare. Besides several BSRs, a gas seepage was also found. As shown by the data, both the BSR and gas seepage are all related with local geological structures, such as mud diapir, anticline, and fault-controlled graben-like structure. However, similar structural "anomalies" are quite common in the tectonically very active Okinawa Trough region, but very few of them have developed BSR or gas seepage. The article points out that the main reason is probably the low concentration of organic carbon of the sediment in this area. It was speculated that the rare occurrence of gas hydrates in this region is governed by structure-controlled fluid flow. Numerous faults and fractures form a network of high-permeability channels in the sediment and highly fractured igneous basement to allow fluid circulation and ventilation. Fluid flow in this tectonic environment is driven primarily by thermal buoyancy and takes place on a wide range of spatial scales. The fluid flow may play two roles to facilitate hydrate formation: to help gather enough methane into a small area and to modulate the thermal regime.

(Table 1) Stable isotope data of chemoherm carbonates at Hydrate Ridge on the Cascadia continental margin

Two active chemoherm build-ups growing freely up into the oceanic water column, the Pinnacle and the South East-Knoll Chemoherms, have been discovered at Hydrate Ridge on the Cascadia continental margin. These microbially-mediated carbonate formations rise above the seafloor by several tens of meters and display a pinnacle-shaped morphology with steep flanks. The recovered rocks are pure carbonates dominated by aragonite. Based on fabric and mineralogic composition different varieties of authigenic aragonite can be distinguished. Detailed visual and petrographic investigations unambiguously reveal the involvement of microbes during the formation of the carbonates. The fabric of the cryptocrystalline and fibrous aragonite can be described as thrombolitic. Fossilized microbial filaments in the microcrystalline aragonite indicate the intimate relationship between microbes and carbonates. The strongly 13C-depleted carbon isotope values of the samples (as low as -48.1 per mill PDB) are characteristic of methane as the major carbon source for the carbonate formation. The methane-rich fluids from which the carbonates are precipitated originate most probably from a gas reservoir below the bottom-simulating reflector (BSR) and rise through fault systems. The d18O values of the aragonitic chemoherm carbonates are substantially higher (as high as 5.0 per mill PDB) than the expected equilibrium value for an aragonite forming from ambient seawater (3.5 per mill PDB). As a first approximation this indicates formation from glacial ocean water but other factors are considered as well. A conceptual model is presented for the precipitation of these chemoherm carbonates based on in situ observations and the detailed petrographic investigation of the carbonates. This model explains the function of the consortium of archaea and sulfate-reducing bacteria that grows on the carbonates performing anaerobic oxidation of methane (AOM) and enabling the precipitation of the chemoherms above the seafloor surrounded by oxic seawater. Beggiatoa mats growing on the surface of the chemoherms oxidize the sulfide provided by sulfate-dependent anaerobic oxidation of methane within an oxic environment. The contact between Beggiatoa and the underlying microbial consortium represents the interface between the overlying oxic water column and an anoxic micro-environment where carbonate formation takes place.