Volcanic Aerosol Evolution: Model vs. In Situ Sampling

Volcanoes are the most significant non-anthropogenic source of tropospheric aerosols. Aerosol samples were collected at different distances from 92°C fumarolic source at Poás Volcano. Aerosols were captured on TEM grids coated by a thin C-film using a specially designed collector. In the sampling, grids were exposed to the plume for 30-second intervals then sealed and frozen to prevent reaction before ATEM analysis to determine aerosol size and chemistry. Gas composition was established using gas chromatography, wet chemistry techniques, AAS and Ion Chromatography on samples collected directly from a fumarolic vent. SO₂ flux was measured remotely by COSPEC. A Gaussian plume dispersion model was used to model concentrations of the gases at different distances down-wind. Calculated mixing ratios of air and the initial gas species were used as input to the thermo-chemical model GASWORKS (Symonds and Reed, Am. Jour. Sci., 1993). Modeled products were compared with measured aerosol compositions. Aerosols predicted to precipitate out of the plume one meter above the fumarole are [CaSO₄, Fe₂.3SO₄, H₂SO₄, MgF₂. Na₂SO₄, silica, water]. Where the plume leaves the confines of the crater, 380 meters distant, the predicted aerosols are the same, excepting FeF₃ replacing Fe₂.3SO₄. Collected aerosols show considerable compositional differences between the sampling locations and are more complex than those predicted. Aerosols from the fumarole consist of [Fe +/- Si,S,Cl], [S +/- O] and [Si +/- O]. Aerosols collected on the crater rim consist of the same plus [O,Na,Mg,Ca], [O,Si,Cl +/- Fe], [Fe,O,F] and [S,O +/- Mg,Ca]. The comparison between results obtained by the equilibrium gas model and the actual aerosol compositions shows that an assumption of chemical and thermal equilibrium evolution is invalid. The complex aerosols collected contrast the simple formulae predicted. These findings show that complex, non-equilibrium chemical reactions take place immediately upon volcanic gas interaction with air, and continue as the plume dissipates. The finding of rapid formation of aerosols at very short distances from source suggests that remote sensing measurements of volatiles made at great distances are likely underestimates.