Sources of limestone dissolution from surface water-groundwater interaction in the carbonate critical zone

Dissolution of carbonate minerals in karst aquifers has long been recognized to result from recharge of surface water undersaturated with respect to calcite from carbonic acid produced by hydration of dissolved atmospheric and respired CO2. However, dissolution also results from additional acids produced by reactions of redox sensitive solutes in the subsurface, which may represent a source of CO2 to Earth's atmosphere. Because the magnitude of dissolution by these additional acids is poorly constrained, we compare here fractions of dissolution from initial surface water undersaturation and subsurface redox reactions. Estimates are based on chemical mixing and geochemical (PHREEQC) modeling of time series measurements of water compositions at a spring vent that receives surface water during stream flooding and a stream sink-rise system in north-central Florida. During a single spring reversal, 9.2 x 10(5) kg of limestone dissolved. At the stream sink-rise system, where subsurface residence times are shorter than during the spring reversal, both limestone dissolution (10(2)-10(4) kg) and precipitation (10(2)-10(5) kg) occur as water flows through the conduits with residence times ranging from 10 to 70 h. At both sites, maximum calcite dissolution rates of similar to 10 mu M hr(-1) occurs at subsurface residence times between 30 and 50 h. For subsurface residence time > similar to 20-60 h, the models indicate that production of additional acid in the subsurface is required for similar to 53 +/- 7% of dissolution. Oxidation of organic carbon, ammonium, pyrite, iron, and/or manganese produce sufficient acid for additional dissolution, but dissolved oxygen is insufficient for these reactions, indicating some acidity is generated under anerobic conditions. Dissolution caused by subsurface reactions in our samples represents mobilization of 20 x 10(4)-30 x 10(4) kg of CO2 via remineralization of organic carbon or carbonate dissolution by nitric and sulfuric acids. Acid produced by subsurface redox reactions during surface water-groundwater interactions, including non-carbonic acids, are important in conduit development and carbon cycling in the carbonate critical zone.