Observation and modelling of ozone-destructive halogen chemistry
in a passive degassing volcanic plume
Authors: Surl Luke , Roberts Tjarda , Bekki Slimane 
Published: March 2021

Abstract. Volcanoes emit halogens into the atmosphere that undergo chemical cycling in plumes and cause destruction of ozone. The impacts of volcanic halogens are inherently difficult to measure at volcanoes, and the complexity of the chemistry, coupled with the mixing and dispersion of the plume, makes the system challenging to model numerically. We present aircraft observations of the Mount Etna plume in the summer of 2012, when the volcano was passively degassing. Measurements of SO2 – an indicator of plume intensity – and ozone were made in the plume a few 10s of km from the source, revealing a strong negative correlation between ozone and SO2 levels. From these observations we estimate a mean in-plume ozone loss rate of 1.3 × 10−5 molecules of O3 per second per molecule of SO2. This value is similar to observation-derived estimates reported very close to the Mount Etna vents, indicating continual ozone loss in the plume up to at least 10's km downwind. The chemically reactive plume is simulated using a new numerical 3D model WRF-Chem Volcano (WCV), a version of WRF-Chem we have modified to incorporate volcanic emissions (including HBr and HCl) and multi-phase halogen chemistry. We used nested grids to model the plume close to the volcano at 1 km. The focus is on the early evolution of passively degassing plumes aged less than one hour and up to 10's km downwind. The model reproduces the so-called bromine explosion: the daytime bromine activation process by which HBr in the plume is converted to other more reactive forms that continuously cycle in the plume. These forms include the radical BrO, a species whose ratio with SO2 is commonly measured in volcanic plumes as an indicator of halogen ozone-destroying chemistry. We track the modelled partitioning of bromine between its forms. The model yields in-plume BrO / SO2 ratios (around 10−4 mol/mol) similar to those observed previously in Etna plumes. The modelled BrO / SO2 is lower in plumes which are more dilute (e.g. at greater windspeed). It is also slightly lower in plumes in the middle of the day compared than in the morning and evening, due to BrO's reaction with diurnally varying HO2. Sensitivity simulations confirm the importance of near-vent products from high temperature chemistry, notably bromine radicals, in initiating the ambient temperature plume halogen cycling. Note also that heterogeneous reactions that activate bromine also activate a small fraction of the emitted chlorine; the resulting production of chlorine radical Cl causes a strong reduction in the methane lifetime and increasing formation of HCHO in the plume. Modelled rates of ozone depletion are found to be similar to those derived from aircraft observations. Ozone destruction in the model is controlled by the processes that recycle bromine, with about three-quarters of this recycling occurring via reactions between halogen oxide radicals. Through sensitivity simulations, a relationship between the magnitude of halogen emissions and ozone loss is established. Volcanic halogens cycling impacts profoundly the overall plume chemistry, notably hydrogen oxide radicals (HOx), nitrogen oxides (NOx), sulfur, and mercury chemistry. In the model, it depletes HOx within the plume, increasing the lifetime of SO2 and hence slowing sulfate aerosol formation. Halogen chemistry also promotes the conversion of NOx into nitric acid (HNO3). This, along with the displacement of nitrate out of background aerosols in the plume, results in enhance HNO3 levels and an almost total depletion of NOx in the plume. The halogen-mercury model scheme is simple but includes newly-identified photo-reductions of mercury halides. With this set-up, the mercury oxidation is found to be slow and in near-balance with the photo-reduction in the plume. Overall, the model findings demonstrate that halogen chemistry has to be considered for a complete understanding of sulfur, HOx, reactive nitrogen, and mercury chemistry, and of the formation of sulfate particles in volcanic plumes.