Direct observation of anisotropic growth of water films on minerals driven by defects and surface tension.

Knowledge of the occurrences of water films on minerals is critical for global biogeochemical and atmospheric processes, including element cycling and ice nucleation. The underlying mechanisms controlling water film growth are, however, misunderstood. Using infrared nanospectroscopy, amplitude-modulated atomic force microscopy, and molecular simulations, we show how water films grow from water vapor on hydrophilic mineral nanoparticles. We imaged films with up to four water layers that grow anisotropically over a single face. Growth usually begins from the near edges of a face where defects preferentially capture water vapor. Thicker films produced by condensation cooling completely engulf nanoparticles and form thicker menisci over defects. The high surface tension of water smooths film surfaces and produces films of inhomogeneous thickness. Nanoscale topography and film surface energy thereby control anisotropic distributions and thicknesses of water films on hydrophilic mineral nanoparticles.

X-ray Photoelectron Spectroscopy of Fast-Frozen Hematite Colloids in Aqueous Solutions. 6. Sodium Halide (F-, Cl-, Br-, I-) Ion Binding on Microparticles.

Electrolyte ion binding at mineral surfaces is central to the generation of surface charge and key to electric double-layer formation. X-ray photoelectron spectroscopy of fast-frozen (-170 °C) mineral wet pastes provides a means to study weakly bound electrolyte ions at the mineral/water interface. In this study, we build upon a series of articles devoted to ion binding at hematite (α-Fe2O3) particle surfaces to resolve the nature of sodium halide ion binding. Measurements on micron-sized hematite particles terminated by the charged and amphoteric (012) and the relatively uncharged (001) faces point to the formation of salt loadings of similar composition to those of cryosalts of NaCl, NaBr, NaI, and NaF. These coatings could be likened to those of the better-known hydrohalite (NaCl·2H2O) phase, one that typically forms under concentrated (≫0.1 M) aqueous solutions of NaCl under freezing conditions. As we have previously shown that these reaction products do not occur in nanosized hematite particles, our work points to the involvement of the basal (001) face and/or the juxtaposition of these faces in packed tabular microparticles of hematite (1-3 µm in width) in stabilizing these cryosalts. One possible formation pathway involves first-layer Na+ and Cl- ions serving as an anchoring layer for a topotactic-like growth of amorphous to low-crystalline salt hydrates at the (001) face. Thus, by contrasting reaction products of four sodium halides at surfaces of tabular microparticles of hematite, this work revealed the formation of cryosalt-like solids. The formation of such solids may have especially important ramifications to ice nucleation mechanisms in the atmosphere, as well as in saline permafrosts on Earth and on planet Mars where salt-laden mineral particles prevail.

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.

Thin Ice Films at Mineral Surfaces.

Ice films formed at mineral surfaces are of widespread occurrence in nature and are involved in numerous atmospheric and terrestrial processes. In this study, we studied thin ice films at surfaces of 19 synthetic and natural mineral samples of varied structure and composition. These thin films were formed by sublimation of thicker hexagonal ice overlayers mostly produced by freezing wet pastes of mineral particles at -10 and -50 °C. Vibration spectroscopy revealed that thin ice films contained smaller populations of strongly hydrogen-bonded water molecules than in hexagonal ice and liquid water. Thin ice films at the surfaces of the majority of minerals considered in this work [i.e., metal (oxy)(hydr)oxides, phyllosilicates, silicates, volcanic ash, Arizona Test Dust] produced intense O-H stretching bands at ∼3400 cm(-1), attenuated bands at ∼3200 cm(-1), and liquid-water-like bending band at ∼1640 cm(-1) irrespective of structure and composition. Illite, a nonexpandable phyllosilicate, is the only mineral that stabilized a form of ice that was strongly resilient to sublimation in temperatures as low as -50 °C. As mineral-bound thin ice films are the substrates upon which ice grows from water vapor or aqueous solutions, this study provides new constraints from which their natural occurrences can be understood.

Thin Water Films at Multifaceted Hematite Particle Surfaces.

Mineral surfaces exposed to moist air stabilize nanometer- to micrometer-thick water films. This study resolves the nature of thin water film formation at multifaceted hematite (α-Fe2O3) nanoparticle surfaces with crystallographic faces resolved by selected area electron diffraction. Dynamic vapor adsorption (DVA) in the 0-19 Torr range at 298 K showed that these particles stabilize water films consisting of up to 4-5 monolayers. Modeling of these data predicts water loadings in terms of an "adsorption regime" (up to 16 H2O/nm(2)) involving direct water binding to hematite surface sites, and of a "condensation regime" (up to 34 H2O/nm(2)) involving water binding to hematite-bound water nanoclusters. Vibration spectroscopy identified the predominant hematite surface hydroxo groups (-OH, µ-OH, µ3-OH) through which first layer water molecules formed hydrogen bonds, as well as surface iron sites directly coordinating water molecules (i.e., as geminal η-(OH2)2 sites). Chemometric analyses of the vibration spectra also revealed a strong correspondence in the response of hematite surface hydroxo groups to DVA-derived water loadings. These findings point to a near-saturation of the hydrogen-bonding environment of surface hydroxo groups at a partial water vapor pressure of ∼8 Torr (∼40% relative humidity). Classical molecular dynamics (MD) resolved the interfacial water structures and hydrogen bonding populations at five representative crystallographic faces expressed in these nanoparticles. Simulations of single oriented slabs underscored the individual roles of all (hydro)oxo groups in donating and accepting hydrogen bonds with first layer water in the "adsorption regime". These analyses pointed to the preponderance of hydrogen bond-donating -OH groups in the stabilization of thin water films. Contributions of µ-OH and µ3-OH groups are secondary, yet remain essential in the stabilization of thin water films. MD simulations also helped resolve crystallographic controls on water-water interactions occurring in the "condensation regime". Water-water hydrogen bond populations are greatest on the (001) face, and decrease in importance in the order (001) > (012) ≈ (110) > (014) ≫ (100). Simulations of a single (∼5 nm × âˆ¼ 6 nm × âˆ¼ 6 nm) nanometric hematite particle terminated by the (001), (110), (012), and (100) faces also highlighted the key roles that sites at particle edges play in interconnecting thin water films grown along contiguous crystallographic faces. Hydroxo-water hydrogen bond populations showed that edges were the preferential loci of binding. These simulations also suggested that equilibration times for water binding at edges were slower than on crystallographic faces. In this regard, edges, and by extension roughened surfaces, are expected to play commanding roles in the stabilization of thin water films. Thus, in focusing on the properties of nanometric-thick water layers at hematite surfaces, this study revealed the nature of interactions between water and multifaced particle surfaces. Our results pave the way for furthering our understanding of mineral-thin water film interfacial structure and reactivity on a broader range of materials.