Reactive bromine chemistry in Mount Etna's volcanic plume: the influence of total Br, high-temperature processing, aerosol loading and plume–air mixing

T J Roberts,L Jourdain,R S Martin

doi:10.5194/acp-14-11201-2014

Abstract

Abstract. Volcanic emissions present a source of reactive halogens to the troposphere, through rapid plume chemistry that converts the emitted HBr to more reactive forms such as BrO. The nature of this process is poorly quantified, yet is of interest in order to understand volcanic impacts on the troposphere, and infer volcanic activity from volcanic gas measurements (i.e. BrO / SO2 ratios). Recent observations from Etna report an initial increase and subsequent plateau or decline in BrO / SO2 ratios with distance downwind. We present daytime PlumeChem model simulations that reproduce and explain the reported trend in BrO / SO2 at Etna including the initial rise and subsequent plateau. Suites of model simulations also investigate the influences of volcanic aerosol loading, bromine emission, and plume–air mixing rate on the downwind plume chemistry. Emitted volcanic HBr is converted into reactive bromine by autocatalytic bromine chemistry cycles whose onset is accelerated by the model high-temperature initialisation. These rapid chemistry cycles also impact the reactive bromine speciation through inter-conversion of Br, Br2, BrO, BrONO2, BrCl, HOBr. We predict a new evolution of Br speciation in the plume. BrO, Br2, Br and HBr are the main plume species near downwind whilst BrO and HOBr are present further downwind (where BrONO2 and BrCl also make up a minor fraction). BrNO2 is predicted to be only a relatively minor plume component. The initial rise in BrO / SO2 occurs as ozone is entrained into the plume whose reaction with Br promotes net formation of BrO. Aerosol has a modest impact on BrO / SO2 near-downwind (< ~6 km, ~10 min) at the relatively high loadings considered. The subsequent decline in BrO / SO2 occurs as entrainment of oxidants HO2 and NO2 promotes net formation of HOBr and BrONO2, whilst the plume dispersion dilutes volcanic aerosol so slows the heterogeneous loss rates of these species. A higher volcanic aerosol loading enhances BrO / SO2 in the (> 6 km) downwind plume. Simulations assuming low/medium and high Etna bromine emissions scenarios show that the bromine emission has a greater influence on BrO / SO2 further downwind and a modest impact near downwind, and show either complete or partial conversion of HBr into reactive bromine, respectively, yielding BrO contents that reach up to ~50 or ~20% of total bromine (over a timescale of a few 10 s of minutes). Plume–air mixing non-linearly impacts the downwind BrO / SO2, as shown by simulations with varying plume dispersion, wind speed and volcanic emission flux. Greater volcanic emission flux leads to lower BrO / SO2 ratios near downwind, but also delays the subsequent decline in BrO / SO2, and thus yields higher BrO / SO2 ratios further downwind. We highlight the important role of plume chemistry models for the interpretation of observed changes in BrO / SO2 during/prior to volcanic eruptions, as well as for quantifying volcanic plume impacts on atmospheric chemistry. Simulated plume impacts include ozone, HOx and NOx depletion, the latter converted into HNO3. Partial recovery of ozone occurs with distance downwind, although cumulative ozone loss is ongoing over the 3 h simulations.

Highlights

DOAS measurements show that BrO forms at hundreds of pmol mol−1 to nmol mol−1 mixing ratios just minutes downwind, an order of magnitude higher than that found in the Arctic, where BrO episodes of up to tens of pmol mol−1 cause significant ozone depletion and mercury deposition events (Simpson et al, 2007)
We present a PlumeChem model study of the reactive halogen chemistry of Mt Etna volcano plume that reproduces the recently reported trends in BrO / SO2; namely a rapid increase in the near-downwind followed by stability or decline in the far-downwind plume
Emitted volcanic HBr is converted into reactive bromine by autocatalytic bromine chemistry cycles whose onset is accelerated by the model high-temperature initialisation

Summary

Introduction

The discovery of volcanic BrO (Bobrowski et al, 2003), and its subsequent observation in many volcanic plumes globally (e.g. Oppenheimer et al, 2006; Bobrowski et al, 2007; Bobrowski and Platt, 2007; Kern et al, 2009; Bani et al, 2009; Louban et al, 2009; Theys et al, 2009; Boichu et al, 2011; Heue et al, 2011; Bobrowski and Giuffrida, 2012; Rix et al, 2012; Hörmann et al, 2013; Kelly et al, 2013; Lübcke et al, 2014), demonstrates the reactivity of volcanic halogen emissions in the troposphere. There is potential to use long-term BrO monitoring at volcanoes as an indicator of volcanic activity (Bobrowski and Giuffrida, 2012). There is strong interest in developing models to simulate the formation of reactive bromine (and chlorine) in volcanic plumes, and to predict the downwind impacts from both quiescently degassing volcanoes and episodic eruptions to the troposphere. Studies to date usually use equilibrium models to predict the high-temperature chemistry of the nearvent plume, which is used to initialise kinetic atmospheric chemistry models of the downwind reactive halogen chemistry (Bobrowski et al, 2007; Roberts et al, 2009; von Glasow, 2010; Kelly et al, 2013). See von Glasow et al (2009) for an overview

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