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Geochemical study of water and gas discharging from the deeply incised aquifer system at the Grand Canyon, Arizona, pro- vides a paradigm for understanding complex groundwater mixing phenomena, and Quaternary travertines deposited from cool springs provide a paleohydrologic record of this mixing. Geochem- ical data show that springs have marked compositional variability: those associated with active travertine accumulations (deeply de- rived endogenic waters) are more saline, richer in C02, and elevated in 87Sr/86Sr relative to springs derived dominantly from surface recharge of plateau aquifers (epigenic waters). Endogenic waters and associated travertine are preferentially located along basement-penetrating faults. We propose a model whereby deeply derived fluids are conveyed upward via both magmatism and seis- micity. Our model is supported by: (1) gas analyses from spring waters with high He/Ar and He/N2 and 3He/4He ratios indicating the presence of mantle-derived He; (2) large volumes of travertine and CO2-rich gases in springs recording high CO2 fluxes; and (3) 87Sr/86Sr in these springs that indicate circulation of waters through Precambrian basement. Geochemical trends are explained by mixing of epigenic waters of the Colorado Plateau aquifers with different endogenic end-member waters in different tectonic sub-provinces. Endogenic waters are volumetrically minor but have significant effects on water chemistry. They are an important and largely unrecognized component of the hydrogeochemistry and neotectonics of the southwestern United States. [ABSTRACT FROM AUTHOR]

Unintended release of CO(2) from carbon sequestration reservoirs poses a well-recognized risk to groundwater quality. Research has largely focused on in situ CO(2)-induced pH depression and subsequent trace metal mobilization. In this paper we focus on a second mechanism: upward intrusion of displaced brine or brackish-water into a shallow aquifer as a result of CO(2) injection. Studies of two natural analog sites provide insights into physical and chemical mechanisms controlling both brackish water and CO(2) intrusion into shallow aquifers along fault zones. At the Chimayó, New Mexico site, shallow groundwater near the fault is enriched in CO(2) and, in some places, salinity is significantly elevated. In contrast, at the Springerville, Arizona site CO(2) is leaking upward through brine aquifers but does not appear to be increasing salinity in the shallow aquifer. Using multiphase transport simulations we show conditions under which significant CO(2) can be transported through deep brine aquifers into shallow layers. Only a subset of these conditions favor entrainment of salinity into the shallow aquifer: high aspect-ratio leakage pathways and viscous coupling between the fluid phases. Recognition of the conditions under which salinity is favored to be cotransported with CO(2) into shallow aquifers will be important in environmental risk assessments.