Organic carbon inputs,common ions and degassing: rethinking mixing dissolution in coastal eogenetic carbonate aquifers

Caves deliver freshwater from coastal carbonate landscapes to estuaries but how these caves form and grow remains poorly understood. Models suggest fresh and salt water mixing drives dissolution in eogenetic limestone, but have rarely been validated through sampling of mixing waters. Here we assess controls on carbonate mineral saturation states using new and legacy geochemical data that were collected in vertical profiles through three cenotes and one borehole in the Yucatan Peninsula. Results suggest saturation states are primarily controlled by carbon fluxes rather than mixing. Undersaturation predicted by mixing models that rely on idealized end members is diminished or eliminated when end members are collected from above and below actual mixing zones. Undersaturation due to mixing is limited by CO₂ degassing from fresh water in karst windows, which results in calcite supersaturation. With respect to saline groundwater, controls on capacity for mixing dissolution were more varied. Oxidation of organic carbon increased pCO₂ of saline groundwater in caves (pCO₂ = 10^–2.06 to 10^–0.96 atm) relative to matrix porosity (10^–2.39 atm) and local seawater (10^–3.12 atm). The impact of increased pCO₂ on saturation state, however, depended on the geochemical composition of the saline water and the magnitude of organic carbon oxidation. Carbonate undersaturation due to mixing was limited where gypsum dissolution (Cenote Angelita) or sulfate reduction (Cenote Calica) increased concentrations of common ions (Ca²⁺ or HCO₃^?, respectively). Maximum undersaturation was found to occur in mixtures including saline water that had ion concentrations and ratios similar to seawater, but with moderately elevated pCO₂ (Cenote Eden). Undersaturation, however, was dominated by the initial undersaturation of the saline end member, mixing was irrelevant. Our results add to a growing body of literature that suggests oxidation of organic carbon, and not mixing dissolution, is the dominant control on cave formation and enlargement in coastal eogenetic karst aquifers. Copyright © 2016 John Wiley & Sons, Ltd.