OClO and BrO observations in the volcanic plume of Mt. Etna – implications on the chemistry of chlorine and bromine species in volcanic plumes
Authors: Gliß J. , Bobrowski N. , Vogel L. , Platt U. 
Published: October 2014

Abstract. Spatial and temporal profiles of chlorine dioxide (OClO), bromine monoxide (BrO) and sulphur dioxide (SO2) were measured in the plume of Mt. Etna, Italy, in September 2012 using Multi-Axis-Differential-Optical-Absorption-Spectroscopy (MAX-DOAS). OClO (BrO) was detected in 119 (452) individual measurements covering plume ages up to 6 (23) minutes. The retrieved slant column densities (SCDs) reached values up to 2.0 × 1014 molecules cm−2 (OClO) and 1.1 × 1015 molecules cm−2 (BrO). In addition, the spectra were analysed for signatures of IO, OIO and OBrO, none of these species could be detected. The corresponding detection limits for IO / SO2, OIO / SO2 and OBrO / SO2 were 1.8 × 10−6, 2.0 × 10−5 and 1.1 × 10−5 respectively. The measurements were performed at plume ages (τ) from zero to 23 min downwind the emission source. The chemical variability of BrO and OClO in the plume was studied analysing the OClO / SO2 and BrO / SO2-ratio. A marked increase of both ratios was observed in the young plume (τ < 3 min) and a levelling off at larger plume ages (τ > 3 min) with mean abundances of 3.17 × 10−5 (OClO / SO2), 1.55 × 10−4 (BrO / SO2) and 0.16 (OClO / BrO). Furthermore, enhanced BrO/SO2-ratios were found at the plume edges (by ~30–37%) and a strong indication of enhanced OClO / SO2-ratios as well (~10–250%). A measurement performed in the early morning (05:20–06:20 UTC, sunrise: 04:40 UTC) showed an BrO / SO2-ratio increasing with time until 05:35 UTC and a constant ratio afterwards. Observing this increase was only possible due to a correction for stratospheric BrO signals in the plume spectra. The corresponding OClO / SO2-ratio showed a similar trend stabilising around 06:13 UTC, approximately 40 min later than BrO. This is another strong indication for the photochemical nature of the reactions involved in the formation of oxidised halogens in volcanic plumes. In particular, these findings support the current understanding of the underlying chemistry, namely, that BrO is formed in an autocatalytic reaction mechanism in literature often referred to as "bromine explosion" and that OClO is formed in the "BrO + ClO"-reaction. BrO and OClO concentrations were estimated from the measured SCDs assuming a circular plume shape. In addition, mixing ratios of ClO were determined from the retrieved OClO and BrO-SCDs assuming chemical equilibrium between formation of OClO (BrO + ClO) and its destruction (photolysis). Mean abundances in the young plume (τ<4 min) were BrO = 1.35 ppb, OClO = 300 ppt and ClO = 139 ppt with peak values of 600 ppt (OClO), 2.7 ppb (BrO) and 235 ppt (ClO) respectively. The prevailing Cl-atom concentrations in the plume could be estimated from the rate of increase of OClO and BrO in the young plume and the determined ClO and OClO concentrations. Values between 5.1 × 106 cm−3 (at 40 ppb O3) and 2.1 × 108 cm−3 (at 1 ppb O3) were found. Based on that, a potential – chlorine induced – depletion of tropospheric methane (CH4) in the plume was investigated. CH4-lifetimes between 13 h (at 1 ppb O3) and 23 days (at 40 ppb O3) were found. These are considerably small compared to the atmospheric lifetime of CH4. However, the impact of gaseous chlorine on the CH4-budget in the plume environment was assessed to be relatively small, mainly due to plume dispersion (decrease of Cl number densities) and permanent mixing of the plume with the surrounding atmosphere (net supply of O3 and CH4).