Halogen acids in fumarolic gases of Kilauea volcano

The water-rich condensates of fumarolic gases, obtained from degassing lavas of the 1959–60 eruption of Kilauea volcano, contain unexpectedly high concentrations of hydrofluoric and hydrochloric acids, and thereby suggest that halogens are significant constituents of basaltic magmas. Vents on the pumice hill of Kilauea Iki yielded one sample that contained, in parts per million, 21,000 HF (1.1 N) with 2,920 HCl, and another sample, 20 HF with 70,500 HCl (2.0 N). Samples from vents elsewhere on the volcano had from one-fortieth to one-thousandth as much of the two acids. A rough correlation exists between the temperature of the fumaroles (range 110 to 820°C) and the total concentration of the halogen acids. This correlation is mainly due to progressive dilution of the magmatic halogen acids by water of probable meteoric origin in fumaroles of lower temperatures. Variations in the HF/HCl ratio (range 0.0003 to 7.2) may be explained by means of two different processes whose relative importance cannot be assessed with the data at hand (1). In their migration to the surface, the acid gases may have reacted with the lava to a variable extent owing to the widely different configurations of the several vents (steaming areas in glassy pumice, glowing cracks, and drillhole in lava lake). In the reaction, relatively more HF could have reacted at temperatures around 300°C with the glassy pumice (2). There is some indication that the HF/HCl ratio increases with time,suggesting that the crystallizing lava may have released HCl early, with HF concentrated in the later exhalations. The Br/Cl ratio ranges from 0.0036 down to 0.0014, as compared to 0.0034 of seawater.