Groundwaters of the southern Colorado Plateau–Arizona Transition Zone region are a heterogeneous mixture of chemically diverse waters including meteoric (epigenic) fluids, karst-aquifer waters, and deeply sourced (endogenic) fluids. We investigate the composition of travertine-depositing CO2-rich springs to determine the origin, transport, and mixing of these various components. The San Francisco Mountain recharge area has little surface flow. Instead, waters discharge through major springs hundreds of kilometers away. About 70% (9340 L/s) of the total recharge (13,500 L/s) discharges 100 km to the north in the incised aquifer system at Grand Canyon. Most of this water (85%; 8070 L/s) emerges through two travertine-depositing karst spring systems: Blue Springs (6230 L/s) and Havasu Springs (1840 L/s). About 30% of recharge (4150 L/s) flows to the south and discharges along NW-striking faults in the Arizona Transition Zone, forming the base flow for the Verde River. Geochemical data define regional mixing trends between meteoric recharge and different endogenic end members that range from bicarbonate waters to sulfate waters. Water quality in the region is dictated by the percentage and character of the endogenic inputs that cause a measurable degradation of groundwater quality for water supply.

Sources for the high CO2 include dissolution of limestone and dolostone (Ccarb) and “external carbon” (Cexternal). Cexternal is computed as the bicarbonate alkalinity (dissolved inorganic carbon [DIC]) minus the Ccarb (Cexternal = DIC - Ccarb). Cexternal is deconvolved using carbon isotopes into biogenically derived sedimentary carbon (Corganic) and deep CO2 inputs (Cendogenic). Measured δ13C values are −17‰ to +3‰ versus Pee Dee Belemnite (PDB). Assuming δ13 Ccarb = +2‰, δ13Corganic = −28‰, and δ13 Cendogenic = −5‰, water chemistry mixing models indicate that an average of 42% of the total DIC comes from dissolution of carbonate rocks, 25% from organic carbon, including soil-respired CO2,and 33% from deep (endogenic) sources. Helium isotope values (3He/4He) in gases dissolved in spring waters in the southern Colorado Plateau region range from 0.10 to 1.16 RA (relative to air) indicating that a significant component of the deeply derived fluid is from the mantle (mean of 5% asthenospheric or 10% subcontinental lithospheric mantle source). Measured CO2/3He ratios of 2 × 109 to 1.4 × 1013 are adjusted by removing the proportion of CO2 from Ccarb and Corganic to give values <5 × 1010 for all but four samples. Various mixing models using CO2/3He suggest that the mantle-derived components of the CO2 load are highly variable from spring to spring and may make up an average of ~10% of the total CO2 load of the regional springs. Fluid-rock interactions involving endogenic fluids are suggested by 87Sr/86Sr, δ18O, and other tracers. The endogenic CO2 component, multiplied by discharge for each spring, yields an integrated annual flux of deeply derived CO2 to the groundwater system of ~1.4 × 109 mol/yr. This CO2 emission from the Colorado Plateau region reflects a complex tectonic evolution involving Laramide hydration of the lithosphere above the Farallon slab, addition of fluids from mid-Tertiary mantle tectonism during slab removal, and ongoing fluid movement induced by neotectonic small-scale asthenospheric convection.

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