title: Structure-activity relationships of mineral dusts as heterogeneous nuclei for ammonium sulfate crystallization from supersaturated aqueous solutions.
abstract: Mineral inclusions, present in aqueous atmospheric salt droplets, regulate crystallization when relative humidity decreases by providing a surface for heterogeneous nucleation and thus reducing the critical supersaturation. Although laboratory studies have quantified these processes to some extent, the diverse atmospheric mineralogy presents more chemical systems than practically feasible for direct study. Structure--activity relationships are necessary. To that end, in the present work the interactions of ammonium sulfate with corundum, hematite, mullite, rutile, anatase, and baddeleyite were studied by diffuse reflectance fourier transform infrared spectroscopy (DRIFTS) and by epitaxial modeling. The spectroscopic results show that shifts in sulfate peak positions due to chemisorption are not a correlative indicator of the efficacy of heterogeneous nucleation. In contrast, epitaxial modeling results of unreconstructed surfaces explain the sequence of critical supersaturations for constant particle size. If validated by further work, this computer modeling method would provide an important structure--activity tool for the estimation of heterogeneous nucleation properties of the atmospheric mineralogy.
authors.affiliation: Division of Engineering and Applied Sciences, 29 Oxford Street, Pierce Hall, Room 122, Harvard University, Cambridge, Massachusetts 02138, USA. scot_martin@harvard.edu
authors.forename: S T
authors.initials: ST
authors.lastname: Martin
authors.forename: J
authors.initials: J
authors.lastname: Schlenker
authors.forename: J H
authors.initials: JH
authors.lastname: Chelf
authors.forename: O W
authors.initials: OW
authors.lastname: Duckworth
mesh_terms: D000537:Aluminum Oxide / Q000737:chemistry; D000538:Aluminum Silicates / Q000737:chemistry; D000645:Ammonium Sulfate / Q000737:chemistry*; D003460:Crystallization; D004391:Dust; D005290:Ferric Compounds / Q000737:chemistry; D008903:Minerals / Q000737:chemistry*; D012996:Solutions; D017550:Spectroscopy, Fourier Transform Infrared; D013329:Structure-Activity Relationship; D014025:Titanium / Q000032:analysis / Q000737:chemistry
chemical_list: D000538:Aluminum Silicates; D004391:Dust; D005290:Ferric Compounds; D008903:Minerals; D012996:Solutions; C009495:titanium dioxide; C000499:ferric oxide; C049037:aluminosilicate; D014025:Titanium; D000537:Aluminum Oxide; D000645:Ammonium Sulfate