Abstract:

In Fig. 6 of this paper the authors suggest how condensation corrosion could shape ceiling cupolas. Hot water containing high concentration of carbon dioxide rises to a lake filling the lower part of the cave room. Degassing of CO2 creates a CO2-containing atmosphere, which is heated by the warmer water below and becomes saturated with vapor, which condenses to the cooler wall of the cave, dissolves limestone and flows back to the lake.

If this process would continue in time it would be perfect to shape large cupolas. However, it does not because condensation stops when the temperature of the cave walls approaches that of the heated air. The reason is that condensation of water at the cave wall releases heat of condensation of 2.45 kJoule/g. This corresponds to an energy flux of 28 Watt/square-meter if a film of 1 mm depth would condensate to the wall in one day. In addition there is also a flux of heat from the warm air to the cave wall. Since the thermal conductivity of limestone (1.3 Watt/m°K) and its thermal diffusivity (5.6 x 10-7 m2/s) are low this heat cannot be rapidly transported into the bedrock, and consequently the temperature of the cave wall rises. Therefore the amount of condensation is reduced. 

One further comment should be given. There have been attempts to measure the effect of condensation corrosion by suspending gypsum plates freely in the air and determining weight loss after a defined time. For the reasons stated above the heat of condensation and the heat flux from the air raise the temperature of such samples much quicker than that of the cave walls. Reliable measurements can only be performed when such samples are fixed to the cave walls by using a high thermal conductivity glue.

A further suggestion to prove condensed water on cave walls is to take samples and analyse them for Ca-concentration and 13 carbon isotopic ratio. Since CO2 comes from the atmosphere exclusively should be below or close to zero, and Ca-concentration should be about 0.6 mmol/liter, when the pCO2 of the cave atmosphere is atmospheric.