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…

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…

Atmospheric Deposition around the Industrial Areas of Milazzo and Priolo Gargallo (Sicily–Italy)—Part A: Major Ions

The chemical composition of rainwater was studied in two highly-industrialised areas in Sicily (southern Italy), between June 2018 and July 2019. The study areas were characterised by large oil refining plants and other industrial hubs whose processes contribute to the release of large amounts of gaseous species that can affect the chemical composition of atmospheric deposition As in most of the Mediterranean area, rainwater acidity (ranging in the study area between 3.9 and 8.3) was buffered by the dissolution of abundant geogenic carbonate aerosol. In particular, calcium and magnesium cations showed the highest pH-neutralizing factor, with ~92% of the acidity brought by SO42− and NO…

Geochemical survey of Levante Bay, Vulcano Island (Italy), a natural laboratory for the study of ocean acidification

Abstract Shallow submarine gas vents in Levante Bay, Vulcano Island (Italy), emit around 3.6t CO2 per day providing a natural laboratory for the study of biogeochemical processes related to seabed CO2 leaks and ocean acidification. The main physico-chemical parameters (T, pH and Eh) were measured at more than 70 stations with 40 seawater samples were collected for chemical analyses. The main gas vent area had high concentrations of dissolved hydrothermal gases, low pH and negative redox values all of which returned to normal seawater values at distances of about 400 m from the main vents. Much of the bay around the vents is corrosive to calcium carbonate; the north shore has a gradient in s…

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…

Sulphur-gas concentrations in volcanic and geothermal areas in Italy and Greece: Characterising potential human exposures and risks

Abstract Passive samplers were used to measure the atmospheric concentrations of SO 2 naturally emitted at three volcanoes in Italy (Etna, Vulcano and Stromboli) and of H 2 S naturally emitted at three volcanic/geothermal areas in Greece (Milos, Santorini and Nisyros). The measured concentrations and dispersion patterns varied with the strength of the source (open conduits or fumaroles), the meteorological conditions and the area topography. At Etna, Vulcano and Stromboli, SO 2 concentrations reach values that are dangerous to people affected by bronchial asthma or lung diseases (> 1000 μg m − 3 ). H 2 S values measured at Nisyros also exceed the limit considered safe for the same group of …

Isotopic composition of the precipitations in the central Mediterranean: Origin marks and orographic precipitation effects

The isotopic composition of the rainfall in northwestern Sicily (Italy, central Mediterranean) was investigated in the period February 2002 to March 2003. A rain gauge network was installed and sampled monthly. The monthly values of the D and 18O ratios showed a wide range that reflected seasonal climatic variations. Mean weighted values were used to define an isotopic model of precipitation. Temporal variations in deuterium excess were also investigated. Using mean volume weighted values, the Local Meteoric Water Line (LMWL) can be represented by the equation: δD = 4.7δ18O - 8.2 (r2 = 0.96). Deuterium excess (d = δD - 8δ18O) was found to be strongly related to orography. The coastline samp…

Isotopic composition of single rain events in the central Mediterranean

[1] The ratios of stable isotopes of single rain events were investigated during the period October 2005 to September 2006 in the central Mediterranean. Clear seasonal trends were identified in both oxygen isotope ratios and the deuterium-excess parameter, and these were ascribed to the dominant circulation systems during both cold and hot intraannual periods. Rain events were classified on the basis of the origin of rain-bearing systems. Air masses coming from the south usually give rise to rainwater with a low deuterium excess. Air masses coming from the north and the northeast are often dry and cold, and are associated with high evaporation from the Mediterranean Sea that occurs under is…

Melt inclusions track melt evolution and degassing of Etnean magmas in the last 15 ka

We present major elements compositions and volatiles contents of olivine-hosted melt inclusions from Etna volcano (Italy), which extend the existing database with the aim of interpreting the chemical variability of Etnean magmas over the last 15 ka. Olivine phenocrysts were selected from the most primitive Fall Stratified (FS) eruptive products of picritic composition (Mg# = 67–70, Fo 89–91 ), the Mt. Spagnolo eccentric lavas (Mg# = 52–64, Fo 82–88 ) and among the more recent 2002–2013 eruptive products (Mg# = 33–53, Fo 68–83 ). Crystal fractionation and degassing processes were modeled at temperatures of 1050–1300 °C, pressures <500 MPa, and oxygen fugacity between 1 and 2 log units abo…

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"

Leachate analyses of volcanic ashes from Stromboli volcano: A proxy for the volcanic gas plume composition?

[1] Many volcanoes show a change in chemical composition of the gas phase prior to periods of eruptive activity. Fine-grained tephra erupted from active vents and transported through volcanic plumes can adsorb, and therefore rapidly scavenge, volatile elements such as sulfur, halogens, and metal species in the form of soluble salts adhering to ash surfaces. Analysis of such water-soluble surface materials is a suitable supplement for remote monitoring of volcanic gases at inaccessible volcanoes. In this work, ash samples of the 2004 to 2009 eruptive activity of Stromboli volcano were sampled, leached, and analyzed for major and trace elements. Data analysis and interpretation was focused on…

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) …

Melt inclusions constrain S behaviour and redox conditions in Etnean magmas

Mount Etna is a complex magmatic system characterized by a continuous variability both in terms of eruptive style and composition of erupted products. Currently, its volcanic activity is marked by high gas fluxes (of above all SO2), both during eruptive and non-eruptive periods. In this study, we have studied the volatile contents and Fe speciation of olivine-hosted melt inclusions from 6 eruptions of the last 15 ky, mainly to investigate the behaviour of S during ascent and differentiation of Etnean magmas. Samples selected come from the FS eruption which is the oldest and most primitive (picritic composition, Fo91), the Mt Spagnolo and from more recent eruptions: 2002/3, 2006, 2008, and 2…

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…