Carbon dioxide clathrate
||This article may be too technical for most readers to understand. (June 2012)|
Carbon dioxide hydrate is a Type I gas clathrate (Sloan 1998). However, there has been some experimental evidence for the development of a metastable Type II phase at temperature near the ice melting point (Fleyfel and Devlin 1990, Staykova et al. 2003). The clathrate is a snow like substance that can exist below 283K (10°C) at a range of pressures of carbon dioxide. It is quite likely to be important on Mars due to the presence of carbon dioxide and ice at low temperatures.
Some history 
The first evidence for the existence of CO2 hydrates dates back to the year 1882, when Wróblewski (1882a, b and c) reported clathrate formation while studying carbonic acid. He noted that gas hydrate was a white material resembling snow, and could be formed by raising the pressure above a certain limit in his H2O - CO2 system. He was the first to estimate the CO2 hydrate composition, finding it to be approximately CO2·8H2O. He also mentions that "...the hydrate is only formed either on the walls of the tube, where the water layer is extremely thin or on the free water surface... (from French)" This already indicates the importance of the surface available for reaction (i.e. the larger the surface the better). Later on, in 1894, Villard deduced the hydrate composition as CO2·6H2O. Three years later, he published the hydrate dissociation curve in the range 267 K to 283 K (Villard 1897). Tamman & Krige (1925) measured the hydrate decomposition curve from 253 K down to 230 K and Frost & Deaton (1946) determined the dissociation pressure between 273 and 283 K. Takenouchi & Kennedy (1965) measured the decomposition curve from 45 bars up to 2 kbar (4.5 to 200 MPa). The CO2 hydrate was classified as a Type I clathrate for the first time by von Stackelberg & Muller (1954).
On Earth, CO2 hydrate is mostly of academic interest. Tim Collett of the United States Geological Survey (USGS) proposed pumping carbon dioxide into subsurface methane clathrates, thereby releasing the methane and storing the carbon dioxide (Michael Marshall, 2009). As of 2009, ConocoPhillips is working on a trial on the Alaska North Slope with the US Department of Energy to release methane in this way, (ConocoPhilips, January 2010, New Scientist, no. 2714, p. 33). At first glance, it seems that the thermodynamic conditions there favor the existence of hydrates, yet given that the pressure is created by sea water rather than by CO2, the hydrate will decompose.
However, it is believed that CO2 clathrate might be of significant importance for planetology. CO2 is an abundant volatile on Mars. It dominates in the atmosphere and covers its polar ice caps much of the time. In the early seventies, the possible existence of CO2 hydrates on Mars was proposed (Miller & Smythe 1970). Recent consideration of the temperature and pressure of the regolith and of the thermally insulating properties of dry ice and CO2 clathrate (Ross and Kargel, 1998) suggested that dry ice, CO2 clathrate, liquid CO2, and carbonated groundwater are common phases, even at Martian temperatures (Lambert and Chamberlain 1978, Hoffman 2000, Kargel et al. 2000).
If CO2 hydrates are present in the Martian polar caps, as some authors suggest (e.g. Clifford et al. 2000, Nye et al. 2000, Jakosky et al. 1995, Hoffman 2000), then the cap will not melt as readily as it would if consisting only of water ice. This is because of the clathrate’s lower thermal conductivity, higher stability under pressure, and higher strength (Durham 1998), as compared to pure water ice.
The question of a possible diurnal and annual CO2 hydrate cycle on Mars remains, since the large temperature amplitudes observed there cause exiting and reentering the clathrate stability field on a daily and seasonal basis. The question is, then, can gas hydrate being deposited on the surface be detected by any means? The OMEGA spectrometer on board Mars Express returned some data, which were used by the OMEGA team to produce CO2 and H2O-based images of the South polar cap. No definitive answer has been rendered with respect to Martian CO2 clathrate formation.
The decomposition of CO2 hydrate is believed to play a significant role in the terraforming processes on Mars, and many of the observed surface features are partly attributed to it. For instance, Musselwhite et al. (2001) argued that the Martian gullies had been formed not by liquid water but by liquid CO2, since the present Martian climate does not allow liquid water existence on the surface in general. This is especially true in the southern hemisphere, where most of the gully structures occur. However, water can be present there as ice Ih, CO2 hydrates or hydrates of other gases (e.g. Max & Clifford 2001, Pellenbarg et al. 2003). All these can be melted under certain conditions and result in gully formation. There might also be liquid water at depths >2 km under the surface (see geotherms in the phase diagram). It is believed that the melting of ground-ice by high heat fluxes formed the Martian chaotic terrains (Mckenzie & Nimmo 1999). Milton (1974) suggested the decomposition of CO2 clathrate caused rapid water outflows and formation of chaotic terrains. Cabrol et al. (1998) proposed that the physical environment and the morphology of the south polar domes on Mars suggest possible cryovolcanism. The surveyed region consisted of 1.5 km-thick-layered deposits covered seasonally by CO2 frost (Thomas et al. 1992) underlain by H2O ice and CO2 hydrate at depths > 10 m (Miller and Smythe, 1970). When the pressure and the temperature are raised above the stability limit, clathrate is decomposed into ice and gases, resulting in explosive eruptions.
Still a lot more examples of the possible importance of the CO2 hydrate on Mars can be given. One thing remains unclear: is it really possible to form hydrate there? Kieffer (2000) suggests no significant amount of clathrates could exist near the surface of Mars. Stewart & Nimmo (2002) find it is extremely unlikely that CO2 clathrate is present in the Martian regolith in quantities that would affect surface modification processes. They argue that long term storage of CO2 hydrate in the crust, hypothetically formed in an ancient warmer climate, is limited by the removal rates in the present climate. Other authors (e.g. Baker et al. 1991) suggest that, if not today, at least in the early Martian geologic history the clathrates may have played an important role for the climate changes there. Since not too much is known about the CO2 hydrates formation and decomposition kinetics, or their physical and structural properties, it becomes clear that all the above mentioned speculations rest on extremely unstable bases.
Phase diagram 
The hydrate structures are stable at different pressure-temperature conditions depending on the guest molecule. Here is given one Mars-related phase diagram of CO2 hydrate, combined with those of pure CO2 and water (Genov 2005). CO2 hydrate has two quadruple points: (I-Lw-H-V) (T = 273.1 K; p = 12.56 bar or 1.256 MPa) and (Lw-H-V-LHC) (T = 283.0 K; p = 44.99 bar or 4.499 MPa) (Sloan, 1998). CO2 itself has a triple point at T = 216.58 K and p = 5.185 bar (518.5 kPa) and a critical point at T = 304.2 K and p = 73.858 bar (7.3858 MPa). The dark gray region (V-I-H) represents the conditions at which CO2 hydrate is stable together with gaseous CO2 and water ice (below 273.15 K). On the horizontal axes the temperature is given in kelvins and degrees Celsius (bottom and top respectively). On the vertical ones are given the pressure (left) and the estimated depth in the Martian regolith (right). The horizontal dashed line at zero depth represents the average Martian surface conditions. The two bent dashed lines show two theoretical Martian geotherms after Stewart & Nimmo (2002) at 30° and 70° latitude.
- Brewer, Peter G.; Gernot Friederich, Edward T. Peltzer, Franklin M. Orr Jr. (7). "Direct Experiments on the Ocean Disposal of Fossil Fuel CO2". Science 284 (5416): 943–945. doi:10.1126/science.284.5416.943. Retrieved 13 September 2011.
- Baker, V. R., Strom, R. G., Gulicvk, V. C., Kargel, J. S., Komatsu, G. & Kale, V. S. (1991) Ancient oceans, ice sheets and the hydrological cycle on Mars. Nature 352, pp. 589–599
- Cabrol, N.A., Grin, E.A., Landheim, R. & McKay, C.P. (1998) Cryovolcanism as a possible origin for pancake-domes in the Mars 98 landing site area: relevance for climate reconstruction and exobiology exploration. In Lunar and Planetary Science XXIX, Lunar and Planetary Institute, Houston, Texas, abstract No. 1249.
- Clifford, S., et al. (2000) The state and future of Mars polar science and exploration. Icarus 144, pp. 210–242.
- ConocoPhillips. Emerging Technologies. Methane Hydrates Production Field Trial data sheet
- Durham W. B. (1998) Factors affecting the rheologic properties of Martian polar ice. In First International Conference on Mars Polar Science ICMPS, Houston, Texas, abstract No. 3024
- Fleyfel, F. and Devlin, J. P. (1991) Carbon Dioxide Clathrate Hydrate Epitaxial Growth: Spectroscopic Evidence for Formation of the Simple Type-II CO2 Hydrate. J. Phys. Chem. 95, pp. 3811–3815
- Frost, E. M. & Deaton, W. M. (1946) Gas hydrate composition and equilibrium data. Oil and Gas Journal, 45, pp. 170–178
- Genov, G. Y. (2005) Physical processes of CO2 hydrate formation and decomposition at conditions relevant to Mars. Ph. D. Thesis, University of Göttingen.
- Hoffman, N. (2000) White Mars: A new model for Mars’ surface and atmosphere based on CO2. Icarus, 146, pp. 326–342.
- Jakosky, B., B. Henderson, & M. Mellon (1995) Chaotic obliquity and the nature of the Martian climate. J. Geophys. Res., 100, pp. 1579–1584
- Kargel, J.S., Tanaka, K.L., Baker, V.R., Komatsu, G. & MacAyeal, D.R., 2000, Formation and dissociation of clathrate hydrates on Mars: Polar caps, northern plains, and highlands. In Lunar and Planetary Science XXX, Lunar and Planetary Institute, Houston, Texas, abstract No. 1891
- Kieffer, H. H. (2000) Clathrates Are Not the Culprit. Science, 287, 5459, pp. 1753–1754
- Lambert, R.S. & Chamberlain, V.E. (1978) CO2 permafrost and Martian topography. Icarus, 34, p. 568–580.
- Marshall, Michael. Ice that burns could be a green fossil fuel New Scientist. 26 March 2009.
- Max, M. D. & Clifford, S. M. (2001) Initiation of Martian outflow channels: Related to the dissociation of gas hydrate? G. Res. Lett. 28, 9, pp. 1787–1790
- Mckenzie, D. & Nimmo, F. (1999) The generation of Martian floods by the melting of ground ice above dykes. Nature, 397, pp. 231–233.
- Miller S. L. & Smythe W. D. (1970) Carbon Dioxide Clathrate in the Martian Ice Cap, Science 170, pp 531–533
- Milton, D.J. (1974) Carbon Dioxide Hydrate and Floods on Mars. Science, 183, pp. 654–656.
- Musselwhite D. S., Swindle T. D. & Lunine J. I. (2001) Liquid CO2 breakout and the formation of recent small gullies on Mars. . In Lunar and Planetary Science XXX, Lunar and Planetary Institute, Houston, Texas, abstract No. 1030
- Nye, J., Durham, W., Schenk, P. & Moore J. (2000) The instability of a south polar cap on Mars composed of carbon dioxide. Icarus 144, pp. 449–455.
- Pellenbarg, R. E., Max, M. D. & Clifford, S. M. (2003) Methane and carbon dioxide hydrates on Mars: Potential origins, distribution, detection, and implications for future in situ resource utilization. J. G. R. - planet, 108, E4, pp. 23–1 – 23-5.
- Ross, R.G. & Kargel, J.S. (1998) Thermal conductivity of solar system ices, with special reference to Martian polar caps. in Schmitt, B., et al., eds., Solar system ices: Dordrecht, Netherlands, Kluwer Academic Publishers, p. 33–62.
- Sloan E. D., Jr. (1998) Clathrate hydrates of natural gases. Second edition, Marcel Dekker Inc.:New York.
- Staykova, D.K., Kuhs, W.F., Salamatin, A.N. & Hansen, Th. (2003) Formation of porous gas hydrates from ice powders: Diffraction experiments and multistage model. J. Phys. Chem. B, 107, 10299- 10311.
- Stewart, S. T. & Nimmo, F. (2002)Surface runoff features on Mars: Testing the carbon dioxide formation hypothesis. J. Geoph. Res. 107, E9, pp. 5069
- Takenouchi, S. & Kennedy, G. C. (1965) Dissociation pressures of the phase CO2·5 ¾ H2O. J. Geology, 73, pp. 383–390
- Tamman, G. & Krige, G. J. (1925) Equilibrium pressures of gas hydrates. Zeit. Anorg. Und Algem. Chem., 146, pp. 179–195 (Original language German)
- Villard, M., P. (1894) On the carbonic hydrate and the composition of gas hydrates. Acad. Sci. Paris, Comptes rendus, 119, pp. 368–371 (Original language French)
- Thomas, P., K. Herkenhoff, A. Howard, B. Murray & S. Squyres (1992) Polar deposits on Mars. In Mars, pp. 767–795. Univ. of Arizona Press, Tucson.
- Villard, M., P. (1897) Experimental study of gas hydrates. Ann. Chim. Phys. (7), 11, pp. 353–360 (Original language French)
- Von Stackelberg, M. & Müller, H. R. (1954) Feste Gashydrate II. Structur und Raumchemie. Z. Electrochem. 58, 25-39.
- Wroblewski, S. (1882a) On the combination of carbonic acid and water. Acad. Sci. Paris, Comptes rendus, 94, pp. 212–213 (Original language French)
- Wroblewski, S. (1882b) On the composition of the hydrate of the carbonic acid. Acad. Sci. Paris, ibid., pp. 954–958 (Original language French)
- Wroblewski, S. (1882c) On the laws of solubility of the carbonic acid in water at high pressures. Acad. Sci. Paris, ibid., pp. 1355–1357 (Original language French)