The influence of gas and humidity on the mineralogy of various salt compositions - implications for natural and technical caverns

Storage caverns are increasingly located in heterogeneous salt deposits and filled with various fluids. The knowledge of phase behaviour in heterogeneous systems of salt, liquid and gas and the requirements for reliable analytical techniques is, therefore, of growing interest. A method that allows for the continuous monitoring of mineral compositions at distinct humidity and gas content using XRD measurements is presented here. Various saliniferous mineral compositions have been investigated in pure CO₂, N₂ or CH₄ atmospheres with varying humidity in a closed chamber. All mineral compositions experience dissolution and/or mineral conversion reaction accompanied by volume loss. Dissolution-recrystallization reactions of complex mineral assemblages involving halite, sylvite, kieserite, carnallite and kainite were observed using this method. For carnallite-rich mineral assemblages, the mineral conversion from carnallite to sylvite was observed when humidity exceeded 50 % RH. In the presence of CO₂, acidification of the aqueous phase occurs which enhances the dissolution rate and reaction kinetics.