Halogen oxide measurements at Masaya Volcano, Nicaragua using active long path differential optical absorption spectroscopy

Abstract

Active Long Path Differential Optical Absorption Spectroscopy (LP-DOAS) measurements of halogen oxides were conducted at Masaya Volcano, in Nicaragua from April 14 to 26, 2007. The active LP-DOAS system allowed night-time halogen measurements and reduced the ClO detection limit by an order of magnitude when compared to previous passive DOAS measurements, as wavelengths below 300 nm could be used for the DOAS retrievals. BrO was detected with an average BrO/SO2 molecular ratio of approximately 3 × 10−5 during the day. However, BrO values were below the detection limit of the instrument for all night-time measurements, a strong indication that BrO is not directly emitted, but rather the result of photochemical formation in the plume itself according to the autocatalytic “bromine explosion” mechanism. Despite the increased sensitivity, both ClO and OClO could not be detected. The achieved upper limits for the X/SO2 ratios were 5 × 10−3 and 7 × 10−6, respectively. A rough calculation suggests that ClO and OClO should be present at similar abundances in volcanic plumes. Since the DOAS technique is orders of magnitude more sensitive for OClO than for ClO, this indicates that OClO should always be detectable in plumes in which ClO is found. However, further LP-DOAS studies are needed to conclusively clarify the role of chlorine oxides in volcanic plumes.