Analytical and Bioanalytical Chemistry

, Volume 409, Issue 25, pp 5975–5985 | Cite as

Development and application of a sampling method for the determination of reactive halogen species in volcanic gas emissions

  • Julian Rüdiger
  • Nicole Bobrowski
  • Marcello Liotta
  • Thorsten HoffmannEmail author
Research Paper


Volcanoes release large amounts of reactive trace gases including sulfur and halogen-containing species into the atmosphere. The knowledge of halogen chemistry in volcanic plumes can deliver information about subsurface processes and is relevant for the understanding of the impact of volcanoes on atmospheric chemistry. In this study, a gas diffusion denuder sampling method using 1,3,5-trimethoxybenzene (1,3,5-TMB)-coated glass tubes for the in situ derivatization of reactive halogen species (RHS) was characterized by a series of laboratory experiments. The coating proved to be applicable to collect selectively gaseous bromine species with oxidation states (OS) of +1 or 0 (such as Br2, BrCl, HOBr, BrO, and BrONO2) while being unreactive to HBr (OS −1). The reaction of 1,3,5-TMB with reactive bromine species forms 1-bromo-2,4,6-TMB—other halogens give corresponding derivatives. Solvent elution of the derivatives followed by analysis with GC-MS results in absolute detection limits of a few nanograms for Br2, Cl2, and I2. In 2015, the technique was applied on volcanic gas plumes at Mt. Etna (Italy) measuring reactive bromine mixing ratios between 0.8 and 7.0 ppbv. Total bromine mixing ratios between 4.7 and 27.5 ppbv were derived from alkaline trap samples, simultaneously taken by a Raschig tube and analyzed with IC and ICP-MS. This leads to the first results of the reactive bromine contribution to total bromine in volcanic emissions, spanning over a range between 12% (±1) and 36% (±2). Our finding is in an agreement with previous model studies, which imply values <44% for plume ages <1 min, which is consistent with the assumed plume age at the sampling sites.

Graphical abstract

Illustration of the measurement procedure for the determination of reactive halogen species in volcanic plumes.


Diffusion denuder Volcanic halogens Molecular bromine Gas chromatography-mass spectrometry 



Julian Rüdiger, Nicole Bobrowski, and Thorsten Hoffmann acknowledge the support by the research center “Volcanoes and Atmosphere in Magmatic, Open Systems” (VAMOS), University of Mainz, Germany. Julian Rüdiger is thankful for the funding from Max Planck Graduate School at the MPIC (MPGS), Mainz, and the support by the Istituto Nazionale di Geofisica e Vulcanologia in Palermo and Catania, Italy.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no competing interests.

Ethical approval

This article does not contain any research with human participants or animals.


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Copyright information

© Springer-Verlag GmbH Germany 2017

Authors and Affiliations

  • Julian Rüdiger
    • 1
  • Nicole Bobrowski
    • 2
    • 3
    • 4
  • Marcello Liotta
    • 5
  • Thorsten Hoffmann
    • 1
    Email author
  1. 1.Institute of Inorganic and Analytical ChemistryJohannes Gutenberg-UniversityMainzGermany
  2. 2.Max Planck Institute for ChemistryMainzGermany
  3. 3.Institute of Environmental PhysicsUniversity of HeidelbergHeidelbergGermany
  4. 4.Former Address: Institute of GeosciencesJohannes Gutenberg-UniversityMainzGermany
  5. 5.Istituto Nazionale di Geofisica e VulcanologiaPalermoItaly

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