The surface chemistry of fresh and weathered historical basalt flows was characterized using surface-sensitive X-ray photoelectron spectroscopy (XPS). Surfaces of unweathered 1987–1990 flows from the Kilauea Volcano, Hawaii, exhibited variable enrichment in Al, Mg, Ca, and F due to the formation of refractory fluoride compounds and pronounced depletion in Si and Fe from the volatilization of SiF₄ and FeF₃ during cooling. These reactions, as predicted from shifts in thermodynamic equilibrium with temperature, are induced by diffusion of HF from the flow interiors to the cooling surface. The lack of Si loss and solid fluoride formation for recent basalts from the Krafla Volcano, Iceland, suggest HF degassing at higher temperatures.

Subsequent short-term subaerial weathering reactions are strongly influenced by the initial surface composition of the flow and therefore its cooling history. Successive samples collected from the 1987 Kilauea flow demonstrated that the fluoridated flow surfaces leached to a predominantly SiO₂ composition by natural weathering within one year. These chemically depleted surfaces were also observed on Hawaiian basalt flows dating back to 1801 AD. Solubility and kinetic models, based on thermodynamic and kinetic data for crystalline AlF₃, MgF₂, and CaF₂, support observed elemental depletion rates due to chemical weathering. Additional loss of alkalis from the Hawaiian basalt occurs from incongruent dissolution of the basalt glass substrate during weathering.