HCl uptake by volcanic ash in the high temperature eruption plume: mechanistic insights

Abstract:

The injection of HCl into the stratosphere by large volcanic eruptions is considered to be little importance, due to the efficient incorporation of the former into hydrometeors within the cooling plume. However, HCl is also adsorbed onto ash surfaces to form soluble –Cl salts within the high temperature core of the eruption plume, and the atmospheric and environmental significance of this process is uncertain. We investigate the capacity of volcanic glasses with tephrite, phonolite, dacite, and rhyolite compositions to adsorb HCl at temperatures of 200-800°C in the presence of SO₂, CO₂ and He. Experiments show that only tephrite and phonolite glasses are significantly reactive to HCl, exhibiting optimal uptake at 400-600°C. The primary reaction product formed during adsorption is NaCl, but Ca-, K-, Al- and Fe- chlorides are also identified. Uptake of HCl by glass surfaces is sustained by interdiffusion of Na⁺ and other Cl-reactive cations with H⁺. Diffusion coefficient calculations yield Na diffusion coefficients for the four glasses, suggesting that the structural role for Na within the glass network governs the capacity for HCl retention. The uptake of HCl under experimental conditions is limited above 500°C by a Cl-induced dehydroxylation process, but the presence of H₂O in the hydrous eruption plume may sustain or enhance adsorption. The experimental data, combined with simulated plume cooling profiles, suggest that HCl adsorption can be a significant scavenging mechanism in large explosive eruptions, particularly in peralkaline systems. The fate of adsorbed HCl is variable; some may be retained on ash surfaces within pyroclastic flows, while chloride-coated ash in the stratosphere could promote the formation of reactive Cl species associated with O₃ destruction. Additionally, Fe- and Cl-bearing salts emplaced on ash surfaces by HCl adsorption within the plume cores of large explosive eruptions may increase the ocean fertilising potential of such events.