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Volcanic plumes are sites of dynamic chemistry involving halogen gases. Here we present new data on the relative abundances of SO2, BrO and OClO gases emitted from Soufrière Hills Volcano [SHV). They were collected during an eruptive hiatus but during sustained degassing at this halogen-rich volcano. By comparison with data from a previous study during an eruptive phase and application of the data and modeling of Villemant et al. (2008), we suggest that, after consideration of errors, either the rate of HBr conversion to BrO is variable, ranging from ∼30% to ∼15%, and/or the relative partitioning of Cl and Br into the gas phase from the melt changes according to eruptive activity. We examine the potential implications of this for fluid-melt partitioning, and compare our results with data from the experimental literature. Our work contributes toward understanding the controls on the BrO/SO2 ratio for volcano monitoring purposes; the changes in plume chemistry with regard to bromine at the onset of lava extrusion may be large and rapid. OClO was detected in the plume at SHV for the first time. This species has only previously been detected in emissions from Mount Etna (using ground-based methods) and from Puyehue Cordon Caulle (using satellite-based methods). No HCHO or NOy species were detected in the spectra.

[1] We report the first combined measurements of the composition and flux of gas emitted from Nyiragongo volcano by ground-based remote-sensing techniques. Ultraviolet spectroscopic measurements made in May/June 2005 and January 2006 indicate average SO(2) emission rates of 38 kg s(-1) and 23 kg s(-1), respectively. Open-path Fourier transform infrared spectroscopic measurements obtained in May/June 2005, January 2006, and June 2007 indicate average molar proportions of 70, 24, 4.6, 0.87, 0.26, 0.11, and 0.0016% for H(2)O, CO(2), SO(2), CO, HCl, HF, and OCS, respectively. The composition of the plume was remarkably similar in 2005, 2006, and 2007, with little temporal variation in proportions of CO(2), SO(2), and CO, in particular, on the scale of seconds or days or even between the three field campaigns that span a period of 24 months. This stability persisted despite a wide range of degassing behaviors on the surface of the summit crater's lava lake ( including discrete strombolian bursts and lava fountains) and variations in the SO(2) emission rate. We explain these observations by a regime of steady state degassing in which bubbles nucleate and ascend in chemical equilibrium with the convecting magma. Short-term ( seconds to minutes) temporal fluctuations in the SO(2)-HCl-HF composition were observed, and these are attributed to shallow degassing processes.