Bobrowski, Nicole

Volcanic degassing provides important information for the assessment of volcanic hazards. Santa Ana and San Miguel are open vent volcanoes along the Central American Volcanic Arc–CAVA, where the magmatism, basaltic to dacitic, is related to the near-orthogonal convergence of the Caribbean Plate and the subducting Cocos Plate. Both volcanoes are the most active ones in El Salvador with recent eruptive events in October 2005 (Santa Ana) and December 2013 (San Miguel), but still not much data on gas composition and emission are available today. At each volcano, SO2 emissions are regularly monitored using ground-based scanning Differential Optical Absorption Spectrometer (Scan-DOAS) instruments that are part of the global “Network for Observation of Volcanic and Atmospheric Change” (NOVAC). We used the data series from these NOVAC stations in order to retrieve SO2 and minimum bromine emissions, which can be retrieved from the same spectral data for the period 2006–2020 at Santa Ana and 2008–2019 at San Miguel. However, BrO was not detected above the detection limit. SO2 emission ranged from 10 to 7,760 t/d, and from 10 to 5,870 t/d for Santa Ana and San Miguel, respectively. In addition, the SO2 emissions are complemented with in situ plume data collected during regular monitoring surveys (2018–2020) and two field campaigns in El Salvador (2019 and 2020). MultiGAS instruments recorded CO2, SO2, H2S and H2 concentrations. We determined an average CO2/SO2 ratio of 2.9 ± 0.6 when peak SO2 concentration exceeded 15 ppmv at Santa Ana, while at San Miguel the CO2/SO2 ratio was 7.4 ± 1.8, but SO2 levels reached only up to 6.1 ppmv. Taking into account these ratios and the SO2 emissions determined in this study, the resulting CO2 emissions are about one order of magnitude higher than those determined so far for the two volcanoes. During the two field campaigns Raschig tubes (active alkaline trap) were used to collect plume samples which were analyzed with IC and ICP-MS to identify and quantify CO2, SO2, HCl, HF, and HBr. Additionally, also 1,3,5-trimethoxybenzene (TMB)-coated denuders were applied and subsequently analyzed by GC-MS to determine the sum of the reactive halogen species (RHS: including Cl2, Br2 , interhalogens, hypohalous acids). The RHS to sulfur ratios at Santa Ana and San Miguel lie in the range of 10−5. Although no new insights could be gained regarding changes with volcanic activity, we present the most comprehensive gas geochemical data set of Santa Ana and San Miguel volcanoes, leading to a solid data baseline for future monitoring purposes at both volcanoes and their improved estimate of CO2, SO2 and halogens emissions. Determining the reactive fraction of halogens is a first step towards a better understanding of their effects on the atmosphere.

Bromine monoxide (BrO) and sulphur dioxide (SO2) are two gases frequently observed in volcanic plumes by spectroscopic techniques capable of continuous gas monitoring like, e.g., Differential Optical Absorption Spectroscopy (DOAS). The spatio-temporal resolution of DOAS measurements, however, only allows to determine average gas fluxes (minutes to hours resolution). In particular, it is insufficient to record two-dimensional images of SO2 and BrO in real-time (seconds time resolution). Thus, it is impossible to resolve details of chemical conversions of reactive plume constituents. However, these details are vital for further understanding reactive halogen chemistry in volcanic plumes. Therefore, instruments that combine high spatio-temporal resolution and high gas sensitivity and selectivity are required. In addition, these instruments must be robust and compact to be suitable for measurements in harsh and remote volcanic environments. Imaging Fabry-Pérot interferometer (FPI) correlation spectroscopy (IFPICS) is a novel technique for atmospheric trace gas imaging. It allows measuring atmospheric gas column density (CD) distributions with a high spatial and temporal resolution, while at the same time providing selectivity and sensitivity comparable to DOAS measurements. IFPICS uses the periodic transmission spectrum of an FPI, that is matched to the periodic narrowband (vibrational) absorption features of the target trace gas. Recently, IFPICS has been successfully applied to volcanic SO2. Here we demonstrate the applicability of IFPICS to much weaker (about two orders of magnitude) trace gas optical densities, such as that of BrO in volcanic plumes. Due to its high reactivity, BrO is extremely difficult to handle in the laboratory. Thus, based on the similarity of the UV absorption cross sections, we used formaldehyde (HCHO) as a spectral proxy for BrO in instrument characterization measurements. Furthermore, we present recent advances in SO2 IFPICS measurements and simultaneous measurements of SO2 and BrO from a field campaign at Mt Etna in July 2021. We find photon shot-noise limited detection limits of 4.7 × 1017 molec s0.5 cm−2 for SO2 and of 8.9 × 1014 molec s0.5 cm−2 for BrO at a spatial resolution of 512 × 512 pixels and 200 × 200 pixels, respectively. Furthermore, an estimate for the BrO to SO2 ratio (around 10–4) in the volcanic plume is given. The prototype instrument presented here provides spatially resolved measurements of the reactive volcanic plume component BrO. The temporal resolution of our approach allows studies of chemical conversions inside volcanic plumes on their intrinsic timescale.

We investigate effects of the three-dimensional (3D) structure of volcanic plumes on the retrieval results of satellite and ground-based UV–Vis observations. For the analysis of such measurements, 1D scenarios are usually assumed (the atmospheric properties only depend on altitude). While 1D assumptions are well suited for the analysis of many atmospheric phenomena, they are usually less appropriate for narrow trace gas plumes. For UV–Vis satellite instruments with large ground pixel sizes like the Global Ozone Monitoring Experiment-2 (GOME-2), the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) or the Ozone Monitoring Instrument (OMI), 3D effects are of minor importance, but usually these observations are not sensitive to small volcanic plumes. In contrast, observations of the TROPOspheric Monitoring Instrument (TROPOMI) on board Sentinel-5P have a much smaller ground pixel size (3.5 × 5.5 km2). Thus, on the one hand, TROPOMI can detect much smaller plumes than previous instruments. On the other hand, 3D effects become more important, because the TROPOMI ground pixel size is smaller than the height of the troposphere and also smaller than horizontal atmospheric photon path lengths in the UV–Vis spectral range. In this study we investigate the following 3D effects using Monte Carlo radiative transfer simulations: (1) the light-mixing effect caused by horizontal photon paths, (2) the saturation effect for strong SO2 absorption, (3) geometric effects related to slant illumination and viewing angles and (4) plume side-effects related to slant illumination angles and photons reaching the sensor from the sides of volcanic plumes. The first two effects especially can lead to a strong and systematic underestimation of the true trace gas content if 1D retrievals are applied (more than 50 % for the light-mixing effect and up to 100 % for the saturation effect). Besides the atmospheric radiative transfer, the saturation effect also affects the spectral retrievals. Geometric effects have a weaker influence on the quantitative analyses but can lead to a spatial smearing of elevated plumes or even to virtual double plumes. Plume side-effects are small for short wavelengths but can become large for longer wavelengths (up to 100 % for slant viewing and illumination angles). For ground-based observations, most of the above-mentioned 3D effects are not important because of the narrow field of view (FOV) and the closer distance between the instrument and the volcanic plume. However, the light-mixing effect shows a similar strong dependence on the horizontal plume extension as for satellite observations and should be taken into account for the analysis of ground-based observations.

Bromine monoxide (BrO) is a key radical in the atmosphere, influencing the chemical state of the atmosphere, most notably the abundance of ozone (O3). O3 depletion caused by the release of bromine has been observed and modeled in polar regions, salt pans, and in particular inside volcanic plumes. Furthermore, the molar ratio of BrO and SO2 – which can be detected simultaneously via spectroscopic measurements using the differential optical absorption spectroscopy (DOAS) method – is a proxy for the magmatic composition of a volcano and potentially an eruption forecast parameter. The detection of BrO in volcanic plumes from satellite spectroscopic observations is limited by the precision and sensitivity of the retrieval, which so far only allowed for the detection of BrO during major eruptions. The unprecedented spatial resolution of up to 3.5 km×5.5 km and the high signal-to-noise ratio of the TROPOspheric Monitoring Instrument (TROPOMI) on board Sentinel-5 Precursor (S-5P) enable observing and monitoring volcanic bromine release globally even for minor eruptions or even quiescent degassing. In this study, we investigate how far the BrO retrieval can be improved using TROPOMI data and how well BrO can be detected, even in small eruptions and during quiescent volcanic degassing. There are two steps for which improvements in accuracy are investigated and applied: the improvement and quantitative determination of (1) the detection limit of the DOAS BrO column retrieval and (2) the correction of the non-volcanic background BrO signal. First, the DOAS retrieval settings are varied, and their influence on accuracy and precision is investigated with respect to the detection limit and potential systematic influences. Based on these results, we propose a dedicated DOAS evaluation scheme optimized for the detection of BrO in volcanic plumes. For the DOAS retrieval, we propose the use of a large fit window from 323–360 nm, yielding a statistical uncertainty lower by a factor of 1.8 compared to previous BrO DOAS algorithms while not enhancing systematic influences. Second, the effect of the background BrO is reduced by a latitude-dependent empirical correction scheme correlated to cloud information as well as information on the O3 column. Via these improvements, the combined statistical and systematic uncertainties in the resulting BrO vertical column density is on the order of . We present a new and accurate retrieval algorithm of BrO columns from TROPOMI observations which allows for the detection of even slightly enhanced BrO amounts inside minor eruptive plumes of bromine-rich volcanoes. While designed specifically for TROPOMI observations, the retrieval algorithm is in general also applicable to other hyperspectral satellite observations. However, some parts might require adaptation.

Remote sensing (RS) of volcanic gases has become a central tool for studying volcanic activity. For instance, ultraviolet (UV) skylight spectroscopy with grating spectrographs (GS) enables SO2 (and, under favourable conditions, BrO) quantification in volcanic plumes from autonomous platforms at safe distances. These measurements can serve volcanic monitoring and they cover all stages of volcanic activity in long measurement time series, which substantially contributes to the refinement of theories on volcanic degassing. Infrared (IR) remote sensing techniques are able to measure further volcanic gases (e.g., HF, HCl, CO2, CO). However, the employed Fourier transform spectrometers (FTSs) are intrinsically intricate and, due to limited resolving power or light throughput, mostly rely on either lamps, direct sun, or hot lava as light source, usually limiting measurements to individual field campaigns. We show that many limitations of grating spectrographs and Fourier transform spectrometer measurements can be overcome by Fabry-Perot interferometer (FPI) based spectrograph implementations. Compared to grating spectrographs and Fourier transform spectrometers, Fabry-Perot interferometer spectrographs reach a 1-3 orders of magnitude higher spectral resolution and superior light throughput with compact and stable set-ups. This leads to 1) enhanced sensitivity and selectivity of the spectral trace gas detection, 2) enables the measurement of so far undetected volcanic plume constituents [e.g., hydroxyl (OH) or sulfanyl (SH)], and 3) extends the range of gases that can be measured continuously using the sky as light source. Here, we present measurements with a shoe-box-size Fabry-Perot interferometer spectrograph (resolving power of ca. 150000), performed in the crater of Nyiragongo volcano. By analysing the light of a ultraviolet light emitting diode that is sent through the hot gas emission of an active lava flow, we reach an OH detection limit of about 20 ppb, which is orders of magnitude lower than the mixing ratios predicted by high-temperature chemical models. Furthermore, we introduce example calculations that demonstrate the feasibility of skylight-based remote sensing of HF and HCl in the short-wave infrared with Fabry-Perot interferometer spectrographs, which opens the path to continuous monitoring and data acquisition during all stages of volcanic activity. This is only one among many further potential applications of remote sensing of volcanic gases with high spectral resolution.

The study of the chemical composition of volcanic emissions is an important method for obtaining information about volcanic systems and providing indirect and unique insights into magmatic processes. However, there is a non-negligible risk associated with sampling directly at volcanic craters or maintaining geochemical monitoring stations at such locations. Spectroscopic remote sensing methods, in turn, can measure only a few species. Here, drones offer the opportunity to bring measurement systems to the scene. Standard parameters that are commonly measured are SO2 and CO2 concentrations, as well as a number of meteorological parameters. The in-flight transmission of data by radio telemetry plays an important role, since visual localization of the volcanic plume from a distance of several kilometers is practically impossible. Until now, larger and quite cost-intensive drones have been used for this purpose, which must first be transported to the site of operation at great expense. Here, we present the development and successful deployment of a very small drone system (empty weight < 0.9 kg) for chemical characterization of volcanic plumes that can be easily transported on foot to difficult-to-access terrain and, moreover, requires only minimal flight and administrative preparations for operation as an aerial observation platform.

Volatiles released from magma can form bubbles and leave the magma body to eventually mix with atmospheric air. The composition of those volatiles, as derived from measurements made after their emission, is used to draw conclusions on processes in the Earth's interior or their influences on Earth's atmosphere. So far, the discussion of the influence of high-temperature mixing with atmospheric air (in particular oxygen) on the measured volcanic gas composition is almost exclusively based on thermodynamic equilibrium (TE) considerations. By modeling the combined effects of C-H-O-S reaction kinetics, turbulent mixing, and associated cooling during the first seconds after magmatic gas release into the atmosphere we show that the resulting gas compositions generally do not represent TE states, with individual species (e.g., CO, H2, H2S, OCS, SO3, HO2, H2O2) deviating by orders of magnitude from equilibrium levels. Besides revealing the chemical details of high-temperature emission processes, our results question common interpretations of volcanic gas studies, particularly affecting the present understanding of auto-catalytic conversion of volcanic halogen species in the atmosphere and redox state determination from volcanic plume gas measurements.

The origin of magmatic fluids along the East African Rift System (EARS) is a long-lived field of debate in the scientific community. Here, we investigate the chemical composition of the volcanic gas plume and fumaroles at Nyiragongo and Nyamulagira (Democratic Republic of Congo), the only two currently erupting volcanoes set on the Western Branch of the rift. Our results are in line with earlier conceptual models proposing that volcanic gas emissions along the EARS mainly reflect variable contributions of either a Sub-Continental Lithospheric Mantle (SCLM) component or a Depleted Morb Mantle (DMM) component, and deeper fluid. At Nyiragongo and Nyamulagira, our study discards a major contribution of a high 3He/4He mantle plume component in the genesis of volcanic fluids beneath the area. High CO2/3He in fumaroles of both volcanoes is thought to reflect carbonate metasomatism in the lithospheric mantle source. As inferred by previous results obtained on the lava chemistry, this carbonate metasomatism would be more pronounced beneath Nyiragongo. This supports the idea of the presence of distinct metasomes within the lithospheric mantle beneath the Western Branch of the rift.

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. The emissions result in a volcanic plume that includes solid particles, acidic droplets, and gaseous species. The plume-rain interaction imprints the chemical signature of the volcanic emissions in falling raindrops. The most acidic gases (e.g. HCl and HI) readily dissolve in water, and so their ratio in rain samples reflects that of the volcanic plume. The transport of HF is mediated by the large amount of silicate particles generated at the lava–air interface. SO2 is only partially converted into H2SO4 that dissolves in water. The refractory elements dissolved in rain samples derive from the dissolution of silicate particles, and most of them (Al, Mg, Ca, Fe, Be, Ti, Mn, and Sr) are present at exactly the same molar ratios as in the rocks as well as rare earth elements (REEs). By contrast, Li, Na, K, Cr, Ni, Cu, Zn, Rb, Cd, Sb, Te, Cs, Tl, Pb, and Bi are enriched relative to the whole-rock composition, suggesting that they are volatilized during magma degassing. After correcting for the dissolution of silicate particles, we can define the relative volatility of these elements. The comparison with other volcanoes on the Pb emissions highlights the effect of oxygen fugacity in determining its volatility.

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 gas diffusion denuder sampling followed by gas chromatography–mass spectrometry (GC-MS) analysis, whereas the total halogens and sulfur concentrations were obtained by alkaline trap sampling with subsequent ion chromatography (IC) and inductively coupled plasma mass spectrometry (ICP-MS) measurements. Both ground and airborne sampling with an unoccupied aerial vehicle (carrying a denuder sampler in combination with an electrochemical SO2 sensor) were conducted at varying distances from the crater rim. The in situ measurements were accompanied by remote sensing observations (differential optical absorption spectroscopy; DOAS). The reactive fraction of bromine increased from 0.20 ± 0.13 at the crater rim to 0.76 ± 0.26 at 2.8 km downwind, whereas chlorine showed an increase in the reactive fraction from (2.7 ± 0.7) × 10−4 to (11 ± 3) × 10−4 in the first 750 m. Additionally, a reactive iodine fraction of 0.3 at the crater rim and 0.9 at 2.8 km downwind was measured. No significant change in BrO / SO2 molar ratios was observed with the estimated age of the observed plume ranging from 1.4 to 11.1 min. This study presents a large complementary data set of different halogen compounds at Masaya volcano that allowed for the quantification of reactive bromine in the plume of Masaya volcano at different plume ages. With the observed field data, a chemistry box model (Chemistry As A Boxmodel Application Module Efficiently Calculating the Chemistry of the Atmosphere; CAABA/MECCA) allowed us to reproduce the observed trend in the ratio of the reactive bromine to total bromine ratio. An observed contribution of BrO to the reactive bromine fraction of about 10 % was reproduced in the first few minutes of the model run.