Particle Size Controls on Water Adsorption and Condensation Regimes at Mineral Surfaces.

Atmospheric water vapour interacting with hydrophilic mineral surfaces can produce water films of various thicknesses and structures. In this work we show that mineral particle size controls water loadings achieved by water vapour deposition on 21 contrasting mineral samples exposed to atmospheres of up to ~16 Torr water (70% relative humidity at 25 °C). Submicrometer-sized particles hosted up to ~5 monolayers of water, while micrometer-sized particles up to several thousand monolayers. All films exhibited vibrational spectroscopic signals akin to liquid water, yet with a disrupted network of hydrogen bonds. Water adsorption isotherms were predicted using models (1- or 2- term Freundlich and Do-Do models) describing an adsorption and a condensation regime, respectively pertaining to the binding of water onto mineral surfaces and water film growth by water-water interactions. The Hygroscopic Growth Theory could also account for the particle size dependence on condensable water loadings under the premise that larger particles have a greater propensity of exhibiting of surface regions and interparticle spacings facilitating water condensation reactions. Our work should impact our ability to predict water film formation at mineral surfaces of contrasting particle sizes, and should thus contribute to our understanding of water adsorption and condensation reactions occuring in nature.