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. The chemical characterization of volcanic gas emissionsgives insights into the interior of volcanoes. Bromine species have beencorrelated with changes in the activity of a volcano. In order to exploitthe volcanic bromine gases, we need to understand what happens to them afterthey are outgassed into the atmosphere. This study aims to shed light on the conversion of bromospecies afterdegassing. The method presented here allows for the specific analysis of gaseoushydrogen bromide (HBr) in volcanic environments. HBr is immobilized byreaction with 5,6-epoxy-5,6-dihydro-[1,10]-phenanthroline (EP), which actsas an inner coating inside of diffusion denuder tubes (in situ derivatization). Thederivative is analyzed by high-performance liquid chromatography coupled toelectrospray ionization mass spectrometry (HPLC-ESI-MS). The collection efficiency for HBr (99.5 %), the collection efficiency for HBralongside HCl (98.1 %), and the relative standard deviation of comparablesamples (8 %) have been investigated. The comparison of the newdenuder-based method and Raschig tubes as alkaline traps resulted on averagein a relative bias between both methods of 10 ± 6 %. The denuder sampling setup was applied in the plume of Masaya (Nicaragua) in2016. HBr concentrations in the range between 0.44 and 1.97 ppb weremeasured with limits of detection and quantification below 0.1 and 0.3 ppbrespectively. The relative contribution of HBr as a fraction of totalbromine decreased from 75 ± 11 % at the Santiago crater (214 m distanceto the volcanic emission source) to 36 ± 8 % on the Nindiri rim (740 mdistance). A comparison between our data and the previously calculated HBr, based onthe CAABA/MECCA box model, showed a slightly higher trend for the HBrfraction on average than expected from the model. Data gained from this newmethod can further refine model runs in the future.

atmospheric measurement techniques

Bromine speciation in volcanic plumes: new in situ derivatization LC-MS method for the determination of gaseous hydrogen bromide by gas diffusion denuder sampling