Evolution of CO2, SO2, HCl, and HNO3in the volcanic plumes from Etna

The volcanic plumes from degassing Etna (Italy) were extensively probed with instruments onboard the Deutsches Zentrum fur Luft- und Raumfahrt research aircraft Falcon during the contrail, volcano, and cirrus experiment CONCERT on 29/30 September 2011. Up to 10.4 ppmv SO2 and 0.3 ppmv HCl were detected with the atmospheric chemical ionization mass spectrometer AIMS at 3.1 km altitude and 20 km distance to the summit. HNO3 is the dominant reactive nitrogen component in the plumes. Linking aircraft and ground-based observations by Hybrid Single-Particle Lagrangian Integrated Trajectory dispersion modeling, we identify two crater plumes with different compositions primarily injected by the Boc…

Halogen activation in the plume of Masaya volcano: field observations and box model investigations

Volcanic emissions are a source of halogens in the atmosphere. Rapid reactions convert the initially emitted hydrogen halides (HCl, HBr, and HI) into reactive species such as BrO, Br2, BrCl, ClO, OClO, and IO. The activation reaction mechanisms in the plume consume ozone (O3), which is entrained by ambient air that is mixed into the plume. In this study, we present observations of the oxidation of bromine, chlorine, and iodine during the first 11 min following emission, examining the plume from Santiago crater of the Masaya volcano in Nicaragua. Two field campaigns were conducted: one in July 2016 and one in September 2016. The sum of the reactive species of each halogen was determined by g…

Multi-component gas emission measurements of the active lava lake of Nyiragongo, DR Congo

Between 2007 and 2011 four measurement campaigns (June 2007, July 2010, June 2011, and December 2011) were carried out at the crater rim of Nyiragongo volcano, DR Congo. Nyiragongo is one of the most active volcanoes in Africa. The ground-based remote sensing technique Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS), which uses scattered sunlight, the in-situ Multi-Component Gas Analyzer System (Multi-GAS) and alkaline impregnated filter were simultaneously applied during all field trips. The bromine monoxide to sulfur dioxide (BrO/SO2) and carbon dioxide to sulfur dioxide (CO2/SO2) molar ratios were determined, among other ratios. During the different field trips variati…

Retrieval of absolute SO<sub>2</sub> column amounts from scattered-light spectra – Implications for the evaluation of data from automated DOAS Networks

Abstract. Scanning Differential Optical Absorption Spectroscopy (DOAS) networks using scattered solar radiation have become an increasingly important tool for monitoring volcanic sulphur dioxide (SO2) emissions. In order to get absolute column densities (CDs), the DOAS evaluation requires a Fraunhofer Reference Spectrum (FRS) that is free of absorption structures of the trace gas of interest. At volcanoes, this requirement can be formulated in a weaker form, if there is a plume free viewing direction within the spectra of a scan through the complete sky. In this case, it is possible to use a specific viewing direction (e.g. zenith) as FRS and correcting for possible plume contamination in t…

Mobility of plume-derived volcanogenic elements in meteoric water at Nyiragongo volcano (Congo) inferred from the chemical composition of single rainfall events

The chemical composition of single rainfall events was investigated at Nyiragongo volcano (Democratic Republic of Congo) with the aim of determining the relative contributions of plume-derived elements. The different locations of the sampling sites allowed both plume-affected samples (hereafter referred to as “fumigated samples”) and samples representative of the local background to be collected. The chemical composition of the local background reflects the peculiar geographic features of the area, being influenced by biomass burning, geogenic dust, and biological activity. Conversely, fumigated samples contain large amounts of volcanogenic elements that can be clearly distinguished from th…

BrO formation in volcanic plumes

Volcanoes have only recently been recognized as a potentially major source of reactive bromine species to the atmosphere, following from the detection of bromine monoxide (BrO) in the plume emitted by Soufriere Hills Volcano, Montserrat. However, BrO is not expected to be emitted in significant quantity from magma, presenting a puzzle regarding its formation. We report here new field measurements of the tropospheric plume emitted by Mt. Etna, Italy, which provide the first direct evidence of fast oxidation of halogen species in a volcanic plume, and lead to an explanation of how BrO is generated from magmatic HBr emissions. We show that the timescale of BrO formation (a few minutes after em…

Intercomparison of SO2 camera systems for imaging volcanic gas plumes

Abstract SO 2 camera systems are increasingly being used to image volcanic gas plumes. The ability to derive SO 2 emission rates directly from the acquired imagery at high time resolution allows volcanic process studies that incorporate other high time-resolution datasets. Though the general principles behind the SO 2 camera have remained the same for a number of years, recent advances in CCD technology and an improved understanding of the physics behind the measurements have driven a continuous evolution of the camera systems. Here we present an intercomparison of seven different SO 2 cameras. In the first part of the experiment, the various technical designs are compared and the advantage…

Remote sensing of volcanic CO2, HF, HCl, SO2, and BrO in the downwind plume of Mt. Etna

Remote sensing of the gaseous composition of non-eruptive, passively degassing volcanic plumes can be a tool to gain insight into volcano interior processes. Here, we report on a field study in September 2015 that demonstrates the feasibility of remotely measuring the volcanic enhancements of carbon dioxide (CO2), hydrogen fluoride (HF), hydrogen chloride (HCl), sulfur dioxide (SO2), and bromine monoxide (BrO) in the downwind plume of Mt. Etna using portable and rugged spectroscopic instrumentation. To this end, we operated the Fourier transform spectrometer EM27/SUN for the shortwave-infrared (SWIR) spectral range together with a co-mounted UV spectrometer on a mobile platform in direct-su…

Preliminary results of biomonitoring survey at Virunga Volcanic Province (D.R. Congo), Eastern Africa.

Biomonitoring techniques have been widely used in environmental studies to monitor anthropogenic pollutants. Recently such techniques have been also applied to ascertain the impact of contaminants naturally released by volcanic activity (Calabrese et al., 2015; Arndt et al., 2017). In the present study a biomonitoring survey has been performed in different sites around Nyiragongo and Nyamulagira (D.R. Congo), active volcanoes in the western branch of the East African Rift. We applied both active and passive biomonitoring techniques in order to investigate the release of some harmful chemical elements by Nyiragongo and Nyamulagira: the former was performed by exposing moss-bags (Sphagnum sp.…

Magmatic signature in acid rain at Masaya volcano, Nicaragua: Inferences on element volatility during lava lake degassing

Abstract Major, minor and trace element concentrations of single rainfall events were investigated at Masaya volcano (Nicaragua) in order to determine the relative contributions of volcanogenic elements. Most of the samples were collected in the summit area of the volcano around the Santiago crater, and two samples, representative of the local background, were collected at a 4.3 km upwind site. Samples from the summit are very acidic with pH down to 2.14 and contain large amounts of volcanogenic elements that can be clearly distinguished from the local background. These elements are released into the atmosphere from the continuously degassing lava lake of the Santiago crater, Masaya volcano…

Advances in Bromine Speciation in Volcanic Plumes

Volcanoes are a significant halogen source to the atmosphere. After water, carbon dioxide and sulfur compounds, halogens are often the most abundant gases in volcanic plumes. In the past, less attention was given to the heavy halogens bromine and iodine. However, the discovery of bromine monoxide (BrO) in volcanic plumes led to new interest especially in volcanic bromine chemistry and its impact on atmospheric processes. The BrO detection came along with advances in volcanic remote sensing techniques, in particular, robust DOAS applications and the possibility of continuous measurements by automated instruments located at safe distances from the volcano. As one of the consequences, the volc…

Active alkaline traps to determine acidic-gas ratios in volcanic plumes: Sampling techniques and analytical methods

In situ measurements have been the basis for monitoring volcanic gas emissions for many years and—being complemented by remote sensing techniques—still play an important role to date. Con- cerning in situ techniques for sampling a dilute plume, an increase in accuracy and a reduction of detection limits are still necessary for most gases (e.g., CO2, SO2, HCl, HF, HBr, HI). In this work, the Raschig-Tube tech- nique (RT) is modified and utilized for application on volcanic plumes. The theoretical and experimental absorption properties of the RT and the Drechsel bottle (DB) setups are characterized and both are applied simultaneously to the well-established Filter packs technique (FP) in the …

Supplementary material to "Halogen activation in the plume of Masaya volcano: field observations and box model investigations"

Remote sensing of volcanic CO<sub>2</sub>, HF, HCl, SO<sub>2</sub>, and BrO in the downwind plume of Mt. Etna

Abstract. Remote sensing of the gaseous composition of non-eruptive, passively degassing volcanic plumes can be a tool to gain insight into volcano interior processes. Here, we report on a field study in September 2015 that demonstrates the feasibility of remotely measuring the volcanic enhancements of carbon dioxide (CO2), hydrogen fluoride (HF), hydrogen chloride (HCl), sulfur dioxide (SO2), and bromine monoxide (BrO) in the downwind plume of Mt. Etna using portable and rugged spectroscopic instrumentation. To this end, we operated the Fourier Transform Spectrometer EM27/SUN for the shortwave-infrared (SWIR) spectral range together with a co-mounted UV spectrometer on a mobile platform in…

Continuous SO2 flux measurements for Vulcano Island, Italy

<p>The La Fossa cone of Vulcano Island (Aeolian Archipelago, Italy) is a closed conduit volcano. Today, Vulcano Island is characterized by sulfataric activity, with a large fumarolic field that is mainly located in the summit area. A scanning differential optical absorption spectroscopy instrument designed by the Optical Sensing Group of Chalmers University of Technology in Göteborg, Sweden, was installed in the framework of the European project "Network for Observation of Volcanic and Atmospheric Change", in March 2008. This study presents the first dataset of SO<sub>2</sub> plume fluxes recorded for a closed volcanic system. Between 2008 and 2010, the SO<sub>2</…

Multicopter measurements of volcanic gas emissions at Masaya (Nicaragua), Turrialba (Costa Rica) and Stromboli (Italy) volcanoes: Applications for volcano monitoring and insights into halogen speciation

Abstract. Volcanoes are a natural source of several reactive gases (e.g. sulfur and halogen containing species), as well as non-reactive gases (e.g. carbon dioxide). Besides that, halogen chemistry in volcanic plumes might have important impacts on atmospheric chemistry, carbon to sulfur ratios and sulfur dioxide fluxes are important established parameters to gain information on subsurface processes. In this study we demonstrate the successful deployment of a multirotor UAV (quadcopter) system with custom-made lightweight payloads on board for the compositional analysis and gas flux estimation of volcanic plumes. The various applications and their potential with such new measurement strateg…

Passive degassing at Nyiragongo (D.R. Congo) and Etna (Italy) volcanoes

Volcanoes are well known as an impressive large natural source of trace elements into the troposphere. Etna (Italy) and Nyiragongo (D.R. Congo) are two stratovolcanoes located in different geological settings, both characterized by persistent passive degassing from their summit craters. Here, we present some results on trace element composition in volcanic plume emissions, atmospheric bulk deposition (rainwater) and their uptake by the surrounding vegetation, with the aim to compare and identify differences and similarities between these two volcanoes. Volcanic emissions were sampled by using active filter-packs for acid gases (sulfur and halogens) and specific teflon filters for particulat…

Chlorine isotope composition of volcanic rocks and gases at Stromboli volcano (Aeolian Islands, Italy): Inferences on magmatic degassing prior to 2014 eruption

Abstract Among the magmatic volatiles, chlorine (Cl) is degassed at shallow depths offering the opportunity to investigate the behavior of magmatic degassing close to the surface, and the possible occurrence of chemical and isotopic fractionation related to gas/melt partitioning. However, it is still unclear if the isotopic composition of Cl (δ 37 Cl) can be used as a proxy of magmatic degassing. In this work, we investigate the concentrations of chlorine and sulfur, and the Cl isotope composition of rocks and plume gases collected at Stromboli volcano, Aeolian Islands, Italy. This volcano was chosen because it is characterized by persistent eruptive activity (i.e., Strombolian explosions) …

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 ve…

Reactive halogen chemistry in volcanic plumes

[1] Bromine monoxide (BrO) and sulphur dioxide (SO2) abundances as a function of the distance from the source were measured by ground-based scattered light Multiaxis Differential Optical Absorption Spectroscopy (MAX-DOAS) in the volcanic plumes of Mt. Etna on Sicily, Italy, in August–October 2004 and May 2005 and Villarica in Chile in November 2004. BrO and SO2 spatial distributions in a cross section of Mt. Etna's plume were also determined by Imaging DOAS. We observed an increase in the BrO/SO2 ratio in the plume from below the detection limit near the vent to about 4.5 × 10−4 at 19 km (Mt. Etna) and to about 1.3 × 10−4 at 3 km (Villarica) distance, respectively. Additional attempts were …

Variation of the BrO/SO2 molar ratio in the plume of Tungurahua volcano between 2007 and 2017 and its relationship to volcanic activity

International audience; Recent long-term observations of the bromine monoxide (BrO) to sulphur dioxide (SO2) molar ratio in volcanic plumes have suggested a link between changes in the BrO/SO2 ratio and the volcanic activity. Nevertheless, understanding of the mechanisms determining this link is still limited due to the lack of studies on volcanic bromine release from the melt into the atmosphere. We present the results of 10 years (2007–2017) of observations of the BrO/SO2 molar ratio in the volcanic plume of Tungurahua volcano, Ecuador. Following the nearly continuous eruptive activity from 1999 to 2008, Tungurahua showed alternating phases of eruptive activity separated by periods of qui…

Gas emission strength and evolution of the molar ratio of BrO/SO2in the plume of Nyiragongo in comparison to Etna

Airborne and ground-based differential optical absorption spectroscopy observations have been carried out at the volcano Nyiragongo (Democratic Republic of Congo) to measure SO2 and bromine monoxide (BrO) in the plume in March 2004 and June 2007, respectively. Additionally filter pack and multicomponent gas analyzer system (Multi-GAS) measurements were carried out in June 2007. Our measurements provide valuable information on the chemical composition of the volcanic plume emitted from the lava lake of Nyiragongo. The main interest of this study has been to investigate for the first time the bromine emission flux of Nyiragongo (a rift volcano) and the BrO formation in its volcanic plume. Mea…

Quantification of the depletion of ozone in the plume of Mount Etna

Volcanoes are an important source of inorganic halogen species into the atmosphere. Chemical processing of these species generates oxidised, highly reactive, halogen species which catalyse considerable O3 destruction within volcanic plumes. A campaign of ground-based in situ O3, SO2 and meteorology measurements was undertaken at the summit of Mount Etna volcano in July/August 2012. At the same time, spectroscopic measurements were made of BrO and SO2 columns in the plume downwind. Depletions of ozone were seen at all in-plume measurement locations, with average O3 depletions ranging from 11–35 nmol mol−1 (15–45%). Atmospheric processing times of the plume were estimated to be between 1 and …

New insights into the magmatic-hydrothermal system and volatile budget of Lastarria volcano, Chile: Integrated results from the 2014 IAVCEI CCVG 12th Volcanic Gas Workshop

Recent geophysical evidence for large-scale regional crustal inflation and localized crustal magma intrusion has made Lastarria volcano (northern Chile) the target of numerous geological, geophysical, and geochemical studies. The chemical composition of volcanic gases sampled during discrete campaigns from Lastarria volcano indicated a well-developed hydrothermal system from direct fumarole samples in A.D. 2006, 2008, and 2009, and shallow magma degassing using measurements from in situ plume sampling techniques in 2012. It is unclear if the differences in measured gas compositions and resulting interpretations were due to artifacts of the different sampling methods employed, short-term exc…

Plume composition and volatile flux of Nyamulagira volcano, Democratic Republic of Congo, during birth and evolution of the lava lake, 2014-2015

Very little is known about the volatile element makeup of the gaseous emissions of Nyamulagira volcano. This paper tries to fill this gap by reporting the first gas composition measurements of Nyamulagira’s volcanic plume since the onset of its lava lake activity at the end of 2014. Two field surveys were carried out on 1 November 2014, and 13–15 October 2015. We applied a broad toolbox of volcanic gas composition measurement techniques in order to geochemically characterize Nyamulagira’s plume. Nyamulagira is a significant emitter of SO2, and our measurements confirm this, as we recorded SO2 emissions of up to ~ 14 kt/d during the studied period. In contrast to neighbouring Nyiragongo volc…

Aerial strategies advance volcanic gas measurements at inaccessible, strongly degassing volcanoes

Aerial measurements using unoccupied aerial systems (UAS) transform our ability to measure and monitor volcanic plumes.