Methane clathrate

Methane clathrate (CH4·5.75H2O) or (4CH4·23H2O), also called methane hydrate, hydromethane, methane ice, fire ice, natural gas hydrate, or gas hydrate, is a solid clathrate compound (more specifically, a clathrate hydrate) in which a large amount of methane is trapped within a crystal structure of water, forming a solid similar to ice. Originally thought to occur only in the outer regions of the Solar System, where temperatures are low and water ice is common, significant deposits of methane clathrate have been found under sediments on the ocean floors of the Earth. Methane clathrate (CH4·5.75H2O) or (4CH4·23H2O), also called methane hydrate, hydromethane, methane ice, fire ice, natural gas hydrate, or gas hydrate, is a solid clathrate compound (more specifically, a clathrate hydrate) in which a large amount of methane is trapped within a crystal structure of water, forming a solid similar to ice. Originally thought to occur only in the outer regions of the Solar System, where temperatures are low and water ice is common, significant deposits of methane clathrate have been found under sediments on the ocean floors of the Earth. Methane clathrates are common constituents of the shallow marine geosphere and they occur in deep sedimentary structures and form outcrops on the ocean floor. Methane hydrates are believed to form by the precipitation or crystallisation of methane migrating from deep along geological faults. Precipitation occurs when the methane comes in contact with water within the sea bed subject to temperature and pressure. In 2008, research on Antarctic Vostok and EPICA Dome C ice cores revealed that methane clathrates were also present in deep Antarctic ice cores and record a history of atmospheric methane concentrations, dating to 800,000 years ago. The ice-core methane clathrate record is a primary source of data for global warming research, along with oxygen and carbon dioxide. Methane hydrates were discovered in Russia in the 1960s, and studies for extracting gas from it emerged at the beginning of the 21st century. The nominal methane clathrate hydrate composition is (CH4)4(H2O)23, or 1 mole of methane for every 5.75 moles of water, corresponding to 13.4% methane by mass, although the actual composition is dependent on how many methane molecules fit into the various cage structures of the water lattice. The observed density is around 0.9 g/cm3, which means that methane hydrate will float to the surface of the sea or of a lake unless it is bound in place by being formed in or anchored to sediment. One litre of fully saturated methane clathrate solid would therefore contain about 120 grams of methane (or around 169 litres of methane gas at 0 °C and 1 atm), or one cubic metre of methane clathrate releases about 160 cubic metres of gas. Methane forms a structure I hydrate with two dodecahedral (12 vertices, thus 12 water molecules) and six tetradecahedral (14 water molecules) water cages per unit cell. (Because of sharing of water molecules between cages, there are only 46 water molecules per unit cell.) This compares with a hydration number of 20 for methane in aqueous solution. A methane clathrate MAS NMR spectrum recorded at 275 K and 3.1 MPa shows a peak for each cage type and a separate peak for gas phase methane. In 2003, a clay-methane hydrate intercalate was synthesized in which a methane hydrate complex was introduced at the interlayer of a sodium-rich montmorillonite clay. The upper temperature stability of this phase is similar to that of structure I hydrate. Methane clathrates are restricted to the shallow lithosphere (i.e. < 2,000 m depth). Furthermore, necessary conditions are found only in either continental sedimentary rocks in polar regions where average surface temperatures are less than 0 °C; or in oceanic sediment at water depths greater than 300 m where the bottom water temperature is around 2 °C. In addition, deep fresh water lakes may host gas hydrates as well, e.g. the fresh water Lake Baikal, Siberia. Continental deposits have been located in Siberia and Alaska in sandstone and siltstone beds at less than 800 m depth. Oceanic deposits seem to be widespread in the continental shelf (see Fig.) and can occur within the sediments at depth or close to the sediment-water interface. They may cap even larger deposits of gaseous methane. There are two distinct types of oceanic deposit. The most common is dominated (> 99%) by methane contained in a structure I clathrate and generally found at depth in the sediment. Here, the methane is isotopically light (δ13C < −60‰), which indicates that it is derived from the microbial reduction of CO2. The clathrates in these deep deposits are thought to have formed in situ from the microbially produced methane, since the δ13C values of clathrate and surrounding dissolved methane are similar. However, it is also thought that fresh water used in the pressurization of oil and gas wells in permafrost and along the continental shelves worldwide combines with natural methane to form clathrate at depth and pressure, since methane hydrates are more stable in fresh water than in salt water. Local variations may be very common, since the act of forming hydrate, which extracts pure water from saline formation waters, can often lead to local, and potentially significant, increases in formation water salinity. Hydrates normally exclude the salt in the pore fluid from which it forms, thus they exhibit high electric resistivity just like ice, and sediments containing hydrates have a higher resistivity compared to sediments without gas hydrates (Judge ).:9 These deposits are located within a mid-depth zone around 300–500 m thick in the sediments (the gas hydrate stability zone, or GHSZ) where they coexist with methane dissolved in the fresh, not salt, pore-waters. Above this zone methane is only present in its dissolved form at concentrations that decrease towards the sediment surface. Below it, methane is gaseous. At Blake Ridge on the Atlantic continental rise, the GHSZ started at 190 m depth and continued to 450 m, where it reached equilibrium with the gaseous phase. Measurements indicated that methane occupied 0-9% by volume in the GHSZ, and ~12% in the gaseous zone. In the less common second type found near the sediment surface some samples have a higher proportion of longer-chain hydrocarbons (< 99% methane) contained in a structure II clathrate. Carbon from this type of clathrate is isotopically heavier (δ13C is −29 to −57 ‰) and is thought to have migrated upwards from deep sediments, where methane was formed by thermal decomposition of organic matter. Examples of this type of deposit have been found in the Gulf of Mexico and the Caspian Sea.