The solubility of carbon dioxide (CO 2 ) in underground saline formations is considered to offer significant long-term storage capability to effectively sequester large amounts of anthropogenic CO 2 . Unlike enhanced oil recovery (EOR), geosequestration relies on longer time scales and involves significantly greater volumes of CO 2 . Many geosequestration studies assume that the initial brine state is one containing no dissolved hydrocarbons and, therefore, apply simplistic two-component solubility models starting from a zero dissolved-gas state. Many brine formations near hydrocarbons, however, tend to be close to saturation by methane (CH 4 ). The introduction of excess CO 2 in such systems results in an extraction of the CH 4 into the CO 2 -rich phase, which, in turn, has implications for monitoring of any sequestration project and offers the possibly additional CH 4 mobilization and recovery.