A. J. S. McGonigle

A miniaturised ultraviolet spectrometer for remote sensing of SO2 fluxes: a new tool for volcano surveillance

Abstract For 30 years, the correlation spectrometer (COSPEC) has been the principal tool for remote monitoring of volcanic SO 2 fluxes. During this time, the instrument has played a prominent role in volcanic hazard assessment. COSPEC data also underpin estimates of the global volcanic SO 2 flux to the atmosphere. Though innovative for its time, COSPEC is now outdated in several respects. Here we report the first measurements with a potential replacement, using a low cost, miniature, ultraviolet fibre-optic differential optical absorption spectrometer (mini-DOAS). Field experiments were conducted at Masaya Volcano (Nicaragua) and Soufriere Hills Volcano (Montserrat). The mini-DOAS was operated from a road vehicle and helicopter, and from a fixed position on the ground, indicating fluxes of ∼4 and 1 kg s −1 at Masaya Volcano and Soufriere Hills Volcano, respectively. Side-by-side observations with a COSPEC on Montserrat indicate a comparable sensitivity but the mini-DOAS offers several advantages, including the collection of broadband ultraviolet spectra. It has immense potential for geochemical surveillance at volcanoes worldwide.

Characterization and evolution of tropospheric plumes from Lascar and Villarrica volcanoes, Chile

Chile, reveal that both are significant and sustained emitters of SO2 (28 and 3.7 kg s � 1 , respectively), HCl (9.6 and 1.3 kg s � 1 , respectively), HF (4.5 and 0.3 kg s � 1 , respectively) and near-source sulfate aerosol (0.5 and 0.1 kg s � 1 , respectively). Aerosol plumes are characterized by particle number fluxes (0.08–4.0 mm radius) of � 10 17 s � 1 (Lascar) and � 10 16 s � 1 (Villarrica), the majority of which will act as cloud condensation nuclei at supersaturations >0.1%. Impactor studies suggest that the majority of these particles contain soluble SO4� . Most aerosol size distributions were bimodal with maxima at radii of 0.1–0.2 mm and 0.7–1.5 mm. The mean particle effective radius (Reff) ranged from 0.1 to 1.5 mm, and particle size evolution during transport appears to be controlled by particle water uptake (Villarrica) or loss (Lascar) rather than sulfate production. INDEX TERMS: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801); 0322 Atmospheric Composition and Structure: Constituent sources and sinks; 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry; 8409 Volcanology: Atmospheric effects (0370); 8494 Volcanology: Instruments and techniques; KEYWORDS: volcanoes, degassing, aerosol sulphur dioxide, sulphate, Llaima

Changes in gas composition prior to a minor explosive eruption at Masaya volcano, Nicaragua

Abstract A small explosive eruption at Masaya volcano on 23 April 2001, in which a number of people were injured, was preceded by a distinct change in plume gas compositions. Open-path Fourier transform infrared spectroscopy (FTS) measurements show that the SO 2 /HCl molar ratio increased from 1.8 to 4.6 between April 2000 and April/May 2001. The SO 2 flux decreased from 11 to 4 kg s −1 over this period. We interpret these changes to be the result of scrubbing of water-soluble magmatic gases by a rejuvenated hydrothermal system. A sequence of M 5 earthquakes with epicentres about 7 km from the volcano occurred in July 2000. These may have altered the fracture permeability close to the magmatic conduit, and caused increased magmatic–hydrothermal interaction, leading eventually to the phreatic explosion in 2001. Continuous FTS measurements at suitable volcanoes could provide useful information in support of eruption prediction and forecasting.

Size-Resolved Characterisation of Soluble Ions in the Particles in the Tropospheric Plume of Masaya Volcano, Nicaragua: Origins and Plume Processing

We present the first application of a multi-stage impactor to study volcanic particle emissions to the troposphere from Masaya volcano, Nicaragua. Concentrations of soluble SO42−,Cl−, F−, NO3−, K+, Na+,NH4+, Ca2+ and Mg2+ were determined in 11 size bins from ∼0.07 μm to >25.5 μm. The near-source size distributions showed major modes at 0.5μm (SO42−, H+,NH4+); 0.2 μm and 5.0 μm (Cl−) and 2.0–5.0 μm(F−). K+ and Na+ mirrored the SO42− size-resolvedconcentrations closely, suggesting that these were transported primarily asK2SO4 and Na2SO4 in acidic solution, while Mg2+ andCa2+ presented modes in both <1 μm and >1 μm particles. Changes in relative humidity were studied by comparing daytime (transparent plume) and night-time (condensed plume) results. Enhanced particle growth rates were observed in the night-time plume as well as preferential scavenging of soluble gases, such as HCl, by condensed water. Neutralisation of the acidic aerosol by background ammonia was observed at the crater rim and to a greater extent approximately 15 km downwind of the active crater. We report measurements of re-suspended near-source volcanic dust, which may form a component of the plume downwind. Elevated levels ofSO42−, Cl−, F−,H+, Na+, K+ and Mg2+ were observed around the 10 μm particle diameter in this dust. The volcanic SO42− flux leaving the craterwas ∼0.07 kg s−1.

Ozone depletion in tropospheric volcanic plumes

Ground based remote sensing techniques are used to measure volcanic SO2 fluxes in efforts to characterise volcanic activity. As these measurements are made several km from source there is the potential for in-plume chemical transformation of SO2 to sulphate aerosol (conversion rates are dependent on meteorological conditions), complicating interpretation of observed SO2 flux trends. In contrast to anthropogenic plumes, SO2 lifetimes are poorly constrained for tropospheric volcanic plumes, where the few previous loss rate estimates vary widely (from 99% per hour). We report experiments conducted on the boundary layer plume of Masaya volcano, Nicaragua during the dry season. We found that SO2 fluxes showed negligible variation with plume age or diurnal variations in temperature, relative humidity and insolation, providing confirmation that remote SO2 flux measurements (typically of approximate to500-2000 s old plumes) are reliable proxies for source emissions for ash free tropospheric plumes not emitted into cloud or fog.

Unmanned aerial vehicle measurements of volcanic carbon dioxide fluxes

[i] We report the first measurements of volcanic gases with an unmanned aerial vehicle (UAV). The data were collected at La Fossa crater, Vulcano, Italy, during April 2007, with a helicopter UAV of 3 kg payload, carrying an ultraviolet spectrometer for remotely sensing the SO 2 flux (8.5 Mg d- 1 ), and an infrared spectrometer, and electrochemical sensor assembly for measuring the plume CO 2 /SO 2 ratio; by multiplying these data we compute a CO 2 flux of 170 Mg d -1 . Given the deeper exsolution of carbon dioxide from magma, and its lower solubility in hydro-thermal systems, relative to SO 2 , the ability to remotely measure CO 2 fluxes is significant, with promise to provide more profound geochemical insights, and earlier eruption forecasts, than possible with SO 2 fluxes alone: the most ubiquitous current source of remotely sensed volcanic gas data.

Nitric acid from volcanoes

Abstract Atmospheric cycling of nitric acid and other nitrogen-bearing compounds is an important biogeochemical process, with significant implications for ecosystems and human health. Volcanoes are rarely considered as part of the global nitrogen cycle, but here we show that they release a previously unconsidered flux of HNO3 vapour to the atmosphere. We report the first measurements of nitric acid vapour in the persistent plumes from four volcanoes: Masaya (Nicaragua); Etna (Italy); and Villarrica and Lascar (Chile). Mean near-source volcanic plume concentrations of HNO3 range from 1.8 to 5.6 μmol m−3, an enrichment of one to two orders of magnitude over background (0.1–1.5 μmol m−3). Using mean molar HNO3/SO2 ratios of 0.01, 0.02, 0.05, and 0.07 for Villarrica, Masaya, Etna, and Lascar respectively, combined with SO2 flux measurements, we calculate gaseous HNO3 fluxes from each of these volcanic systems, and extend this to estimate the global flux from high-temperature, non-explosive volcanism to be ∼0.02–0.06 Tg (N) yr−1. While comparatively small on the global scale, this flux could have important implications for regional fixed N budgets. The precise mechanism for the emission of this HNO3 remains unclear but we suggest that thermal nitrogen fixation followed by rapid oxidation of the product NO is most likely. In explosive, ash-rich plumes NO may result from, or at least be supplemented by, production from volcanic lightning rather than thermal N fixation. We have calculated NO production via this route to be of the order of 0.02 Tg (N) yr−1.

Sulphur dioxide fluxes from Mount Etna, Vulcano, and Stromboli measured with an automated scanning ultraviolet spectrometer

We report here SO 2 flux measurements for the southern Italian volcanoes: Mount Etna, Vulcano, and Stromboli made in July 2002 from fixed positions, using an automated plume scanning technique. Spectral data were collected using a miniature ultraviolet spectrometer, and SO 2 column amounts were derived with a differential optical absorption spectroscopy evaluation routine. Scanning through the plume was enabled by a 45° turning mirror affixed to the shaft of a computer controlled stepper motor, so that scattered skylight from incremental angles within the horizon-to-horizon scans was reflected into the field of view of the spectrometer. Each scan lasted ∼5 min and, by combining these data with wind speeds, average fluxes of 940, 14, and 280 Mg d - 1 were obtained for Etna, Vulcano, and Stromboli, respectively. For comparative purposes, conventional road and airborne traverses were also made using this spectrometer, yielding fluxes of 850, 17, and 210 Mg d - 1 . The automated scanning technique has the advantage of obviating the need for time-consuming traverses underneath the plume and is well suited for longer-term telemetered deployments to provide sustained high time resolution flux data.

Sources, size distribution, and downwind grounding of aerosols from Mount Etna

The number concentrations and size distributions of aerosol particles >0.3 mm diameter were measured at the summit of Mount Etna and up to 10 km downwind from the degassing vents during July and August 2004. Aerosol number concentrations reached in excess of 9 106 L1 at summit vents, compared to 4–8 104 L1 in background air. Number concentrations of intermediate size particles were higher in emissions from the Northeast crater compared to other summit crater vents, and chemical composition measurements showed that Northeast crater aerosols contained a higher mineral cation content compared to those from Voragine or Bocca Nuova, attributed to Strombolian or gas puffing activity within the vent. Downwind from the summit the airborne plume was located using zenith sky ultraviolet spectroscopy. Simultaneous measurements indicated a coincidence of elevated ground level aerosol concentrations with overhead SO2, demonstrating rapid downward mixing of the plume onto the lower flanks of the volcano under certain meteorological conditions. At downwind sites the ground level particle number concentrations were elevated in all size fractions, notably in the 2.0–7.5 mm size range. These findings are relevant for assessing human health hazard and suggest that aerosol size distribution measurements may aid volcanic risk management.

Cerium-doped fluoride lasers

In the 30 years since tunable ultraviolet (UV) lasers based on 5d /spl rarr/ 4f transition of trivalent lanthanides doped into solid-state hosts were first demonstrated, tremendous progress has been made in these unique laser systems. Today, cerium-doped fluoride lasers offer wide tunability (280-333 nm), high efficiency (up to 62%) and narrow-band output. These lasers can also be used for femtosecond pulse amplification in the UV. Cerium lasers represent a logical route to generation of tunable UV in all-solid-state systems. In this paper, we review the current state-of-the-art cerium laser crystal development and cerium laser systems.