CO2 hydrate formation and dissociation rates: Application to Mars

CO2 clathrate hydrate is a crystalline material composed of water cages around a CO2 molecule. CO2 gas hydrates are naturally occurring on Earth and are a likely phase on Mars as well as other cold planetary bodies. CO2 hydrates have minor effects on terrestrial atmospheric composition, but may be a major reservoir for greenhouse gases on Mars. In this study, CO2 hydrate formation and dissociation rates were measured experimentally on ultrapure and CO2 infused water ice (ice containing previously trapped CO2 gas bubbles). Overall, increasing pressure and temperature increased CO2 consumption rates, indicating enhanced hydrate formation rates. CO2 consumption and release rates both increased significantly in infused ice experiments as did the overall amount of CO2 consumed. CO2 bubbles formed during freezing of the infused ice likely provided more surface area for hydrate nucleation, increasing the rate of formation. Higher dissociation rates in infused ice experiments compared to ultrapure ice may be due to the higher concentration of hydrate originally formed in the bubble-filled samples. These results suggest that CO2 hydrate formation in natural, gas-rich ice occurs significantly faster than previously assumed. In addition, formation rates would be maximized and dissociation rates minimized at Mars equatorial conditions, perhaps leading to long-term storage of atmospheric CO2 in localized clathrate reservoirs.