Evaporites: Relative humidity control of primary mineral facies revisited

It is widely accepted that the deposition of mineral facies of evaporite basins is controlled by the average annual relative humidity of the contiguous atmosphere, which dictates the equilibrium activity of the evaporating brine. This concept has far reaching implications in salt works and for the investigation of paleoenvironmental settings affecting depositional sequences within evaporite basins. The above concept, which dominated the scientific thought of evaporite basin investigations, suffers from two serious flaws: (a) the assumption of a static decoupled atmosphere and (b) the total neglect of energy input and thermodynamic feedbacks resulting from evaporation suppression. The present investigation will resolve the underlying mechanisms controlling the equilibrium activity of hypersaline solutions using a theoretical framework that combines energy and mass transport across the surface-atmosphere boundary. Calculations of the equilibrium activity of hypersaline solutions under isothermal conditions, as implied in the original concept, are not in line with the basic physical principles defining heat and mass exchange across the brine-atmosphere boundary and lead to substantial overestimation of actual evaporation and the activity itself. It is demonstrated that in addition to atmospheric relative humidity, the activity of hypersaline solutions is determined by numerous meteorological forcings along with hydrological, geochemical, and thermodynamic feedback mechanisms. Evaporation suppression resulting from a drop in brine activity causes substantial increase in brine temperature, which enhances vapour pressure differential across the interface, leading to more evaporation. This negative feedback shifts the brine activity downward for equilibrium to be attained. It is also demonstrated that evaporation from a brine surface usually proceeds when the relative humidity of the contiguous atmosphere is similar or even higher than that of the brine due to energy input and the strong negative feedback caused by evaporation suppression. The present investigation re-establishes a new paradigm concerning the processes controlling evaporite basin sedimentation and palaeoclimate reconstruction as deduced from evaporite/hypersaline basin deposits. Findings have operational ramifications in the industrial applications of dissolved salt mineral extraction.