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RESEARCH PRODUCT

Processes affecting the stable isotope composition of calcite during precipitation on the surface of stalagmites: Laboratory experiments investigating the isotope exchange between DIC in the solution layer on top of a speleothem and the CO2 of the cave atmosphere

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Abstract We present a theoretical derivation of the exchange time, τex, needed to establish isotopic equilibrium between atmospheric CO2 in a cave and HCO3− dissolved in a thin water film covering the surface of a speleothem. The result is τ ex = τ red ex · [ HCO 3 - ] K H · p CO 2 cave , where τ red ex depends on the depth, a, of the water film and on temperature. [ HCO 3 - ] is the concentration of bicarbonate, p CO 2 cave the partial pressure of CO2, and KH is Henry’s constant. To test the theory we prepared stagnant or flowing thin films of a NaHCO3 solution and exposed them at 20 °C to an CO2 containing atmosphere of p CO 2 500, 12,500, or 25,000 ppmV and defined isotope composition. The δ13C and δ18O values of the DIC in the solution were measured as a function of the exposure time. For stagnant films with depths between 0.06 and 0.2 cm the δ13C values exhibit an exponential approach towards isotope equilibrium with the atmospheric CO2 with exchange time, τex. The δ18O values first evolve towards isotopic equilibrium with atmospheric CO2, reach a minimum value and then drift away from the isotopic equilibrium with atmospheric CO2 approaching a steady state caused by isotopic exchange of oxygen with water. The experimental findings are in satisfactory agreement with the theoretical predictions. To further investigate isotope evolution in cave analogue conditions, a water film containing 5 mmol/L of NaHCO3 with a depth of 0.013 cm flowing down an inclined borosilicate glass plate was exposed to an atmosphere with p CO 2  = 500 ppmV at a temperature of 20 °C. The δ13C and δ18O values were measured as a function of flow (exposure) time, t. The isotope compositions in the DIC of the water film decrease linear in time by δ DIC ( t ) = δ DIC ( 0 ) - ( δ DIC ( 0 ) - δ DIC ( ∞ ) ) · t / τ ex where δ DIC ( 0 ) is the initial isotope composition of dissolved inorganic carbon (DIC) in the water film and δ DIC ( ∞ ) its final value. From these data an exchange time τex of ca. 7000 s was obtained, in satisfactory agreement with the theoretical predictions. The exchange times can be calculated by τ ex = τ red ex · [ HCO 3 - ] K H · p CO 2 cave , where τ red ex is given by the theory as function of temperature and the depth, a, of the water film. This way it is possible to obtain exchange times for various conditions of stalagmite growth as they occur in caves.