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Roberts, T. J
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- PublicationRestrictedValidation of a novel Multi-Gas sensor for volcanic HCl alongside H2S and SO2 at Mt. Etna(2017)
; ; ; ; ; ; ; ; ; ; ; ; ; ; ;; ; ; ; ;; ; ; ; ;Volcanic gas emission measurements inform predictions of hazard and atmospheric impacts. For these measurements, Multi-Gas sensors provide low-cost in situ monitoring of gas composition but to date have lacked the ability to detect halogens. Here, two Multi-Gas instruments characterized passive outgassing emissions from Mt. Etna’s (Italy) three summit craters, Voragine (VOR), North-east Crater (NEC) and Bocca Nuova (BN) on 2 October 2013. Signal processing (Sensor Response Model, SRM) approaches are used to analyse H2S/SO2 and HCl/SO2 ratios. A new ability to monitor volcanic HCl using miniature electrochemical sensors is here demonstrated. A “direct-exposure” Multi-Gas instrument contained SO2, H2S and HCl sensors, whose sensitivities, cross-sensitivities and response times were characterized by laboratory calibration. SRM analysis of the field data yields H2S/SO2 and HCl/SO2 molar ratios, finding H2S/SO2 = 0.02 (0.01–0.03), with distinct HCl/SO2 for the VOR, NEC and BN crater emissions of 0.41 (0.38–0.43), 0.58 (0.54–0.60) and 0.20 (0.17–0.33). A second Multi-Gas instrument provided CO2/SO2 and H2O/SO2 and enabled cros comparison of SO2. The Multi-Gas-measured SO2-HCl-H2S CO2-H2O compositions provide insights into volcanic outgassing. H2S/SO2 ratios indicate gas equilibration at slightly below magmatic temperatures, assuming that the magmatic redox state is preserved. Low SO2/HCl alongside low CO2/SO2 indicates a partially outgassed magma source. We highlight the potential for low-cost HCl sensing of H2S-poor HCl rich volcanic emissions elsewhere. Further tests are needed for H2S-rich plumes and for long-term monitoring. Our study brings two new advances to volcano hazard monitoring: real-time in situ measurement of HCl and improved MultiGas SRM measurements of gas ratios.353 5 - PublicationRestrictedGas and aerosol emissions from Villarrica volcano, Chile(2011)
; ; ; ; ; ; ; ; ; ; ;Sawyer, G. M.; Department of Geography, University of Cambridge ;Salerno, G. G.; Istituto Nazionale di Geofisica e Vulcanologia, Sezione Catania, Catania, Italia ;Le Blond, J. S.; Department of Geography, University of Cambridge - Department of Mineralogy, Natural History Museum ;Martin, R. S.; School of Biological and Chemical Sciences, Queen Mary, University of London - Department of Earth Sciences, University of Cambridge ;Spampinato, L.; Istituto Nazionale di Geofisica e Vulcanologia, Sezione Catania, Catania, Italia ;Roberts, T. J; Norwegian Polar Institute, Polar Environmental Centre ;Mather, T. A.; Department of Earth Sciences, University of Oxford ;Witt, M. L. I.; Department of Earth Sciences, University of Oxford ;Tsanev, V. I.; Department of Geography, University of Cambridge ;Oppenheimer, C.; Department of Geography, University of Cambridge; ; ; ; ; ; ; ; ; Here we report results from a multidisciplinary field campaign at Villarrica volcano, Chile, in March 2009. A range of direct sampling and remote sensing techniqueswas employed to assess gas and aerosol emissions from the volcano, and extend the time series of measurements that have been made during recent years. Airborne traverses beneath the plume with an ultraviolet spectrometer yielded an average SO2 flux of 3.7 kg s−1. This value is similar to previous measurements made at Villarrica during periods of quiescent activity. The composition of the plume was measured at the crater rim using electrochemical sensors and, for the first time, open-path Fourier transforminfrared spectroscopy, yielding a composition of 90.5 mol% H2O, 5.7% CO2, 2.6%SO2, 0.9% HCl, 0.3% HF and b0.01% H2S. Comparison with previous gas measurements made between 2000 and 2004 shows a correlation between increased SO2/HCl ratios and periods of increased activity. Base-treated filter packs were also employed during our campaign, yielding molar ratios of HBr/SO2=1.1×10−4, HI/SO2=1.4×10−5 and HNO3/SO2=1.1×10−3 in the gas phase. Our data represent the most comprehensive gas inventory at Villarrica to date, and the first evaluation of HBr and HI emissions from a South American volcano. Sun photometry of the plume showed the near-source aerosol size distributions were bimodal with maxima at b0.1 and ~1 μm. These findings are consistent with results from analyses in 2003. Electron microscope analysis of particulatematter collected on filters showed an abundance of sphericalmicron-sized particles that are rich in Si, Mg and Al. Non-spherical, S-rich particles were also observed.205 28 - PublicationRestrictedThe primary volcanic aerosol emission from Mt Etna: Size-resolved particles with SO 2 and role in plume reactive halogen chemistry(2018)
; ; ; ; ; ; ; ; ; ; ; ; ; ; ;; ; ; ; ; ; ; ; ; ;Volcanoes are an important source of aerosols to the troposphere. Within minutes after emission, volcanic plume aerosol catalyses conversion of co-emitted HBr, HCl into highly reactive halogens (e.g. BrO, OClO) through chemical cycles that cause substantial ozone depletion in the dispersing downwind plume. This study quantifies the sub-to-supramicron primary volcanic aerosol emission (0.2–5 lm diameter) and its role in this process. An in-situ ground-based study at Mt Etna (Italy) during passive degassing co-deployed an optical particle counter and Multi-Gas SO2 sensors at high time resolution (0.1 Hz) enabling to characterise the aerosol number, size-distribution and emission flux. A tri-modal volcanic aerosol size distribution was found, to which lognormal distributions are fitted. Total particle volume correlates to SO2 (as a plume tracer). The measured particle volume:SO2 ratio equates to a sulfate:SO2 ratio of 1–2% at the observed meteorological conditions (40% Relative Humidity). A particle mass flux of 0.7 kg s 1 is calculated for the measured Mt Etna SO2 flux of 1950 tonnes/day. A numerical plume atmospheric chemistry model is used to simulate the role of the hygroscopic primary aerosol surface area and its humidity dependence on volcanic plume BrO and OClO chemistry. As well as predicting volcanic BrO formation and O3 depletion, the model achieves OClO/SO2 in broad quantitative agreement with recently reported Mt Etna observations, with a predicted maximum a few minutes downwind. In addition to humidity – that enhances aerosols surface area for halogen cycling – background ozone is predicted to be an important control on OClO/SO2. Dependence of BrO/SO2 on ambient humidity is rather low near-to-source but increases further downwind. The model plume chemistry also exhibits strong across-plume spatial variations between plume edge and centre.558 7