Dissolved inorganic carbon and stable carbon isotopic evolution of neutral mine drainage interacting with atmospheric CO2(g).

We investigated the spatial variations in the concentrations of dissolved inorganic carbon (DIC), the stable carbon isotopic composition (δ(13)C) of DIC and the δ(13)C of carbonate precipitated from neutral mine drainage interacting with the atmospheric CO2(g). We assessed the chemical, DIC and δ(13)CDIC evolution of the mine drainage and the δ(13)C evolution of carbonate precipitates for a distance of 562 m from the end of an 8 km tunnel that drains a mine. Our results show that as the mine drainage interacts with atmospheric CO2(g) the outgassing of CO2 due to the high initial partial pressure of CO2 (pCO2) causes the DIC to evolve under kinetic conditions followed by equilibration and then under equilibrium conditions. The carbonate evolution was characterized by spatial increases in pH, decreasing concentrations of Ca(2+) and DIC and by the precipitation of carbonate. The δ(13)CDIC showed a larger enrichment from the tunnel exit to 38 m, moderate continuous enrichment to 318 m and almost no enrichment to 562 m. On the other hand, the δ(13)C of the carbonate precipitates also showed large enrichment from the tunnel exit to 38 m, moderate enrichment to 318 m after which the δ(13)C remained nearly constant. The enrichment in the δ(13)C of the DIC and the carbonate precipitates from 0 to 38 m from kinetic fractionation caused by CO2(g) outgassing was followed by a mix of kinetic fractionation and equilibrium fractionation controlled by carbon exchange between DIC and atmospheric CO2(g) to 318 m and then by equilibrium fractionation from 318 to 562 m. From the carbonate evolution in this neutral mine drainage, we estimated that 20% of the carbon was lost via CO2 outgassing, 12% was sequestered in sediments in the drainage ponds from calcite precipitation and the remainder 68% was exported to the local stream.