Characterisation of the magmatic signature in gas emissions from Turrialba Volcano, Costa Rica

Abstract. The equilibrium composition of volcanic gases with their magma is often overprinted by interaction with a shallow hydrothermal system. Identifying the magmatic signature of volcanic gases is critical to relate their composition to properties of the magma (temperature, fO2, gas-melt segregation depth). We report measurements of the chemical composition and flux of the major gas species emitted from Turrialba volcano during March 2013. Measurements were made of two vents in the summit region; one of which opened in 2010 and the other in 2012. We determined an average SO2 flux of 2.40 ± 0.75 kg s−1 using scanning ultraviolet spectroscopy, and molar proportions of H2O, CO2, SO2, HCl, CO and H2 gases of 94.16, 4.03, 1.56, 0.23, 0.003 and 0.009%, respectively, by open-path Fourier transform infrared (FTIR) spectrometry and a multi-species gas sensing system. Together, these data imply fluxes of 41, 4, 0.2, 2 × 10−3 and 5 × 10–4 kg s−1 for H2O, CO2, HCl, CO and H2 respectively. Although H2S was detected, its concentration could not be resolved. HF was not detected. The chemical signature of the gas from both vents was found to be broadly similar. Following the opening of the 2010 and 2012 vents we found limited to negligible interaction of the magmatic gas with the hydrothermal system has occurred and the gas composition of the volcanic plume is broadly representative of equilibrium with the magma. The time evolution of the gas composition, the continuous emission of large quantities of SO2 and the physical evolution of the summit area with new vent opening and more frequent eruptions all point towards a continuous drying of the hydrothermal system at Turrialba's summit at an apparently increasing rate.

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Volatile transport of metals in the andesitic magmatic-hydrothermal system of White Island

10.26686/wgtn.17064629.v1 ◽

2021 ◽

Author(s):

◽

Céline Mandon

Keyword(s):

Hydrothermal System ◽

Crater Lake ◽

Magma Mixing ◽

Aqueous Fluid ◽

Metal Mobility ◽

Volcanic Plume ◽

Volcanic Gases ◽

Volatile Transport ◽

Magmatic Gases ◽

White Island

Volcanic gases observed at active volcanoes originate from the magma at depth. These volatiles exsolve as a result of decompression, crystallization and cooling of the silicate melt. The transport of metals in a magmatic volatile phase arises from complexation with the main volatile species, sulfur and halides. Composition of the magma, temperature, pressure and redox state have thus strong implications on metal mobility in these environments. Moreover, a variety of interactions and phase separations can affect these fluids after exsolution from the parental magma. This thesis aims at constraining the volatile transport of trace metals at White Island, a subduction-related magmatic-hydrothermal system, through a characterization and metal budget of the magmatic reservoir and the different atmospheric discharges. The metal content of the reservoir, as well as the effects of degassing and magma mixing on the magma are explored through the study of ejecta from the 1976-2000 eruptive cycle. CO₂, SO₂ and H₂O are degassing from a mafic melt at ~ 5 km depth, regularly feeding a shallower and evolved reservoir at ~ 800 m. Average contents of 164 ppm of Cu, 73 ppm of Zn, 12 ppm of Pb and 0.4 ppm of Au and Ag were detected in melt inclusions. A fraction of these metals partition into the exsolving aqueous fluid. Onset of magnetite crystallization may trigger exsolution of sulphide melt, found to contain around 30 wt% of Cu, and as much as 36 wt% Ni, 21 wt% Ag, 0.10 wt% Au in small inclusions, representing a considerable source of metals available for an aqueous fluid phase upon resorption. The volatile transport of metals is indicated by their enrichment in a variety of discharges at the surface. The hyperacidic waters of the crater lake absorb metals from the magmatic gases injected at subaqueous vents. Concentrations of ~ 12 ppm of As and Zn, 6 ppm of Cu and Pb were observed. Hydrolysis of the host rock by the reactive waters is responsible for the high cation contents of the fluids. Precipitation of secondary minerals such as silica, anhydrite, gypsum, sulfur and alunite occurs within and underneath the crater lake. The predicted speciation of metals greatly varies, dominated by CuI and FeII chloride complexes in the more reduced environment at the lake bottom, whereas CuII and FeIII are stable in the oxidized surficial waters. Arsenic is mainly present as As(OH)₃ at depth, with H₃AsO₄ dominating at the surface. Ag, Pb and Zn are complexed with chloride, and are not redox dependent. The presence of a body of molten sulfur at the bottom of the lake is indicated by sulfur spherules, both floating at the lake surface and in sediments. Pyrite crystals coat the surface of some globules, and chemical analyses reveal an enrichment in a variety of chalcophile metals (Tl, Sb, Bi, Au, As, Ag. Re, Cu). The volcanic gases emitted at fumaroles are enriched in metals compared to the magma. The effective transport of Se, Te, Sb, B, Au, As, and Bi is indicated by enrichment factors larger than 1000. In contrast, Cu is relatively depleted, suggesting deposition in the subsurface environment. Variations in composition are observed with time, mainly depending on temperature and major composition of the emissions. Values > 100 ppb of Sb, Bi, Ni, Zn, As and Se, > 10 ppb of Te, Pb, and Cu, and up to 8 ppb of Tl were recorded. Chloride is predicted to be the main ligand responsible for metal transport, even at higher temperature. The lack of thermodynamic data for complex solvated metal clusters may nevertheless bias our results. The low temperature of the studied fumaroles (maximum 192.5 °C) is in accordance with the small abundance of sulfides in the sublimates, whereas the high proportion of sulfates indicates oxidized conditions. The volcanic plume is enriched in metals such as Bi, Cd, Tl, Se, Te and Sb. The most common particles emitted are sulfates, halides, silicates, sulphuric acid and Zn ± Cu oxides. Metal emission rates are in the range of 1-10 kg/day for As, Se, Cu and Zn, 0.1-1 kg/day for Pb, Tl and Bi. Emissions of high-temperature magmatic gases are indicated by elevated SO₂/HCl ratio and the presence of Au in the particulate phase. Mass balance calculations in White Island magmatic-hydrothermal system indicate a segregation of around 4900 tons of copper per year, either accumulated from a dense brine at ~ 500 m depth, or deposited by low-density vapors on their way to the surface. Metal-rich sulfide blebs trapped in phenocrysts may also retain Cu at depth. These results thus reinforce the belief that White Island is an actively forming porphyry copper deposit.

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Volatile transport of metals in the andesitic magmatic-hydrothermal system of White Island

10.26686/wgtn.17064629 ◽

2021 ◽

Author(s):

◽

Céline Mandon

Keyword(s):

Hydrothermal System ◽

Crater Lake ◽

Magma Mixing ◽

Aqueous Fluid ◽

Metal Mobility ◽

Volcanic Plume ◽

Volcanic Gases ◽

Volatile Transport ◽

Magmatic Gases ◽

White Island

Volcanic gases observed at active volcanoes originate from the magma at depth. These volatiles exsolve as a result of decompression, crystallization and cooling of the silicate melt. The transport of metals in a magmatic volatile phase arises from complexation with the main volatile species, sulfur and halides. Composition of the magma, temperature, pressure and redox state have thus strong implications on metal mobility in these environments. Moreover, a variety of interactions and phase separations can affect these fluids after exsolution from the parental magma. This thesis aims at constraining the volatile transport of trace metals at White Island, a subduction-related magmatic-hydrothermal system, through a characterization and metal budget of the magmatic reservoir and the different atmospheric discharges. The metal content of the reservoir, as well as the effects of degassing and magma mixing on the magma are explored through the study of ejecta from the 1976-2000 eruptive cycle. CO₂, SO₂ and H₂O are degassing from a mafic melt at ~ 5 km depth, regularly feeding a shallower and evolved reservoir at ~ 800 m. Average contents of 164 ppm of Cu, 73 ppm of Zn, 12 ppm of Pb and 0.4 ppm of Au and Ag were detected in melt inclusions. A fraction of these metals partition into the exsolving aqueous fluid. Onset of magnetite crystallization may trigger exsolution of sulphide melt, found to contain around 30 wt% of Cu, and as much as 36 wt% Ni, 21 wt% Ag, 0.10 wt% Au in small inclusions, representing a considerable source of metals available for an aqueous fluid phase upon resorption. The volatile transport of metals is indicated by their enrichment in a variety of discharges at the surface. The hyperacidic waters of the crater lake absorb metals from the magmatic gases injected at subaqueous vents. Concentrations of ~ 12 ppm of As and Zn, 6 ppm of Cu and Pb were observed. Hydrolysis of the host rock by the reactive waters is responsible for the high cation contents of the fluids. Precipitation of secondary minerals such as silica, anhydrite, gypsum, sulfur and alunite occurs within and underneath the crater lake. The predicted speciation of metals greatly varies, dominated by CuI and FeII chloride complexes in the more reduced environment at the lake bottom, whereas CuII and FeIII are stable in the oxidized surficial waters. Arsenic is mainly present as As(OH)₃ at depth, with H₃AsO₄ dominating at the surface. Ag, Pb and Zn are complexed with chloride, and are not redox dependent. The presence of a body of molten sulfur at the bottom of the lake is indicated by sulfur spherules, both floating at the lake surface and in sediments. Pyrite crystals coat the surface of some globules, and chemical analyses reveal an enrichment in a variety of chalcophile metals (Tl, Sb, Bi, Au, As, Ag. Re, Cu). The volcanic gases emitted at fumaroles are enriched in metals compared to the magma. The effective transport of Se, Te, Sb, B, Au, As, and Bi is indicated by enrichment factors larger than 1000. In contrast, Cu is relatively depleted, suggesting deposition in the subsurface environment. Variations in composition are observed with time, mainly depending on temperature and major composition of the emissions. Values > 100 ppb of Sb, Bi, Ni, Zn, As and Se, > 10 ppb of Te, Pb, and Cu, and up to 8 ppb of Tl were recorded. Chloride is predicted to be the main ligand responsible for metal transport, even at higher temperature. The lack of thermodynamic data for complex solvated metal clusters may nevertheless bias our results. The low temperature of the studied fumaroles (maximum 192.5 °C) is in accordance with the small abundance of sulfides in the sublimates, whereas the high proportion of sulfates indicates oxidized conditions. The volcanic plume is enriched in metals such as Bi, Cd, Tl, Se, Te and Sb. The most common particles emitted are sulfates, halides, silicates, sulphuric acid and Zn ± Cu oxides. Metal emission rates are in the range of 1-10 kg/day for As, Se, Cu and Zn, 0.1-1 kg/day for Pb, Tl and Bi. Emissions of high-temperature magmatic gases are indicated by elevated SO₂/HCl ratio and the presence of Au in the particulate phase. Mass balance calculations in White Island magmatic-hydrothermal system indicate a segregation of around 4900 tons of copper per year, either accumulated from a dense brine at ~ 500 m depth, or deposited by low-density vapors on their way to the surface. Metal-rich sulfide blebs trapped in phenocrysts may also retain Cu at depth. These results thus reinforce the belief that White Island is an actively forming porphyry copper deposit.

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Curating Metal-Organic Frameworks to Compose Robust Gas Sensor Arrays in Dilute Conditions

10.26434/chemrxiv.8179244.v2 ◽

2019 ◽

Author(s):

Arni Sturluson ◽

Rachel Sousa ◽

Yujing Zhang ◽

Melanie T. Huynh ◽

Caleb Laird ◽

...

Keyword(s):

Sensor Array ◽

Gas Sensing ◽

Metal Organic Frameworks ◽

Sensor Arrays ◽

Gas Composition ◽

Composition Space ◽

The Matrix ◽

Metal Organic ◽

Analyte Detection ◽

Value Decomposition

Metal-organic frameworks (MOFs)-- tunable, nano-porous materials-- are alluring recognition elements for gas sensing. Mimicking human olfaction, an array of cross-sensitive, MOF-based sensors could enable analyte detection in complex, variable gas mixtures containing confounding gas species. Herein, we address the question: given a set of MOF candidates and their adsorption properties, how do we select the optimal subset to compose a sensor array that accurately and robustly predicts the gas composition via monitoring the adsorbed mass in each MOF? We first mathematically formulate the MOF-based sensor array problem under dilute conditions. Instructively, the sensor array can be viewed as a linear map from gas composition space to sensor array response space defined by the matrix H of Henry coefficients of the gases in the MOFs. Characterizing this mapping, the singular value decomposition of H is a useful tool for evaluating MOF subsets for sensor arrays, as it determines the sensitivity of the predicted gas composition to measurement error, quantifies the magnitude of the response to changes in composition, and recovers which direction in gas composition space elicits the largest/smallest response. To illustrate, on the basis of experimental adsorption data, we curate MOFs for a sensor array with the objective of determining the concentration of CO2 and SO2 in the gas phase.

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First In-Situ Measurements of Plume Chemistry at Mount Garet Volcano, Island of Gaua (Vanuatu)

Applied Sciences ◽

10.3390/app10207293 ◽

2020 ◽

Vol 10 (20) ◽

pp. 7293

Author(s):

Joao Lages ◽

Yves Moussallam ◽

Philipson Bani ◽

Nial Peters ◽

Alessandro Aiuppa ◽

...

Keyword(s):

High Temperature ◽

Emission Rates ◽

Gas Composition ◽

Gas Analyzer ◽

Total Volatile ◽

Volcanic Gas ◽

So2 Flux ◽

Gas Chemistry

Recent volcanic gas compilations have urged the need to expand in-situ plume measurements to poorly studied, remote volcanic regions. Despite being recognized as one of the main volcanic epicenters on the planet, the Vanuatu arc remains poorly characterized for its subaerial emissions and their chemical imprints. Here, we report on the first plume chemistry data for Mount Garet, on the island of Gaua, one of the few persistent volatile emitters along the Vanuatu arc. Data were collected with a multi-component gas analyzer system (multi-GAS) during a field campaign in December 2018. The average volcanic gas chemistry is characterized by mean molar CO2/SO2, H2O/SO2, H2S/SO2 and H2/SO2 ratios of 0.87, 47.2, 0.13 and 0.01, respectively. Molar proportions in the gas plume are estimated at 95.9 ± 11.6, 1.8 ± 0.5, 2.0 ± 0.01, 0.26 ± 0.02 and 0.06 ± 0.01, for H2O, CO2, SO2, H2S and H2. Using the satellite-based 10-year (2005–2015) averaged SO2 flux of ~434 t d−1 for Mt. Garet, we estimate a total volatile output of about 6482 t d−1 (CO2 ~259 t d−1; H2O ~5758 t d−1; H2S ~30 t d−1; H2 ~0.5 t d−1). This may be representative of a quiescent, yet persistent degassing period at Mt. Garet; whilst, as indicated by SO2 flux reports for the 2009–2010 unrest, emissions can be much higher during eruptive episodes. Our estimated emission rates and gas composition for Mount Garet provide insightful information on volcanic gas signatures in the northernmost part of the Vanuatu Arc Segment. The apparent CO2-poor signature of high-temperature plume degassing at Mount Garet raises questions on the nature of sediments being subducted in this region of the arc and the possible role of the slab as the source of subaerial CO2. In order to better address the dynamics of along-arc volatile recycling, more volcanic gas surveys are needed focusing on northern Vanuatu volcanoes.

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Variability in the Gas Composition of the Popocatépetl Volcanic Plume

Frontiers in Earth Science ◽

10.3389/feart.2019.00114 ◽

2019 ◽

Vol 7 ◽

Cited By ~ 4

Author(s):

Noémie Taquet ◽

Wolfgang Stremme ◽

Michel Grutter ◽

Jorge Baylón ◽

Alejandro Bezanilla ◽

...

Keyword(s):

Volcanic Plume ◽

Gas Composition

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The control of magma crystallinity on the fluctuations in gas composition at open vent basaltic volcanoes

Scientific Reports ◽

10.1038/s41598-020-71667-7 ◽

2020 ◽

Vol 10 (1) ◽

Author(s):

Julia Woitischek ◽

Marie Edmonds ◽

Andrew W. Woods

Keyword(s):

Laboratory Experiments ◽

Volatile Components ◽

Volcanic Gases ◽

Critical Depth ◽

Gas Composition ◽

Gas Migration ◽

Basaltic Volcanoes ◽

Volcanic Conduit ◽

Gas Geochemistry

Abstract Basaltic open vent volcanoes are major global sources of volcanic gases. Many of these volcanoes outgas via intermittent Strombolian-type explosions separated by periods of passive degassing. The gas emitted during the explosions has high molar CO2/SO2 and SO2/HCl ratios, while during the passive degassing these ratios are lower. We present new laboratory experiments in a model volcanic conduit, which suggest that these differences in gas geochemistry are a consequence of gas migration through crystal-rich magma. We show that gas may flow along channels through the particle-laden liquid and, at a critical depth, the gas may displace an overlying crystal-rich plug en masse, producing a growing slug of gas. Owing to the friction on the walls of the conduit, this plug becomes progressively sheared and weakened until gas enriched in the least soluble volatiles breaks through, causing an explosion at the surface. When the gas slug bursts, liquid is drawn up in its wake, which exsolves the more soluble volatile components, which then vent passively at the surface until the next explosive slug-bursting event.

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Inverting for volcanic SO2 flux at high temporal resolution using spaceborne plume imagery and chemistry-transport modelling: the 2010 Eyjafjallajökull eruption case study

Atmospheric Chemistry and Physics ◽

10.5194/acp-13-8569-2013 ◽

2013 ◽

Vol 13 (17) ◽

pp. 8569-8584 ◽

Cited By ~ 33

Author(s):

M. Boichu ◽

L. Menut ◽

D. Khvorostyanov ◽

L. Clarisse ◽

C. Clerbaux ◽

...

Keyword(s):

Temporal Resolution ◽

Spatial Scales ◽

Source Parameters ◽

Volcanic Plume ◽

High Temporal Resolution ◽

Transport Modelling ◽

Important Indicator ◽

So2 Flux ◽

Volcanic Source

Abstract. Depending on the magnitude of their eruptions, volcanoes impact the atmosphere at various temporal and spatial scales. The volcanic source remains a major unknown to rigorously assess these impacts. At the scale of an eruption, the limited knowledge of source parameters, including time variations of erupted mass flux and emission profile, currently represents the greatest issue that limits the reliability of volcanic cloud forecasts. Today, a growing number of satellite and remote sensing observations of distant plumes are becoming available, bringing indirect information on these source terms. Here, we develop an inverse modelling approach combining satellite observations of the volcanic plume with an Eulerian regional chemistry-transport model (CHIMERE) to characterise the volcanic SO2 emissions during an eruptive crisis. The May 2010 eruption of Eyjafjallajökull is a perfect case study to apply this method as the volcano emitted substantial amounts of SO2 during more than a month. We take advantage of the SO2 column amounts provided by a vast set of IASI (Infrared Atmospheric Sounding Interferometer) satellite images to reconstruct retrospectively the time series of the mid-tropospheric SO2 flux emitted by the volcano with a temporal resolution of ~2 h, spanning the period from 1 to 12 May 2010. We show that no a priori knowledge on the SO2 flux is required for this reconstruction. The initialisation of chemistry-transport modelling with this reconstructed source allows for reliable simulation of the evolution of the long-lived tropospheric SO2 cloud over thousands of kilometres. Heterogeneities within the plume, which mainly result from the temporal variability of the emissions, are correctly tracked over a timescale of a week. The robustness of our approach is also demonstrated by the broad similarities between the SO2 flux history determined by this study and the ash discharge behaviour estimated by other means during the phases of high explosive activity at Eyjafjallajökull in May 2010. Finally, we show how a sequential IASI data assimilation allows for a substantial improvement in the forecasts of the location and concentration of the plume compared to an approach assuming constant flux at the source. As the SO2 flux is an important indicator of the volcanic activity, this approach is also of interest to monitor poorly instrumented volcanoes from space.

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New geochemical insights into volcanic degassing

Philosophical Transactions of The Royal Society A Mathematical Physical and Engineering Sciences ◽

10.1098/rsta.2008.0185 ◽

2008 ◽

Vol 366 (1885) ◽

pp. 4559-4579 ◽

Cited By ~ 69

Author(s):

Marie Edmonds

Keyword(s):

Gas Flow ◽

Volcanic Eruptions ◽

Shear Zones ◽

High Temporal Resolution ◽

Volcanic Gases ◽

Spectroscopic Techniques ◽

Volcanic Degassing ◽

Effusive Activity ◽

Gas Loss ◽

Melt Segregation

Magma degassing plays a fundamental role in controlling the style of volcanic eruptions. Whether a volcanic eruption is explosive, or effusive, is of crucial importance to approximately 500 million people living in the shadow of hazardous volcanoes worldwide. Studies of how gases exsolve and separate from magma prior to and during eruptions have been given new impetus by the emergence of more accurate and automated methods to measure volatile species both as volcanic gases and dissolved in the glasses of erupted products. The composition of volcanic gases is dependent on a number of factors, the most important being magma composition and the depth of gas–melt segregation prior to eruption; this latter parameter has proved difficult to constrain in the past, yet is arguably the most critical for controlling eruptive style. Spectroscopic techniques operating in the infrared have proved to be of great value in measuring the composition of gases at high temporal resolution. Such methods, when used in tandem with microanalytical geochemical investigations of erupted products, are leading to better constraints on the depth at which gases are generated and separated from magma. A number of recent studies have focused on transitions between explosive and effusive activity and have led to a better understanding of gas–melt segregation at basaltic volcanoes. Other studies have focused on degassing during intermediate and silicic eruptions. Important new results include the recognition of fluxing by deep-derived gases, which buffer the amount of dissolved volatiles in the melt at shallow depths, and the observation of gas flow up permeable conduit wall shear zones, which may be the primary mechanism for gas loss at the cusp of the most explosive and unpredictable volcanic eruptions. In this paper, I review current and future directions in the field of geochemical studies of volcanic degassing processes and illustrate how the new insights are beginning to change the way in which we understand and classify volcanic eruptions.

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Plume propagation direction determination with SO2 cameras

Atmospheric Measurement Techniques ◽

10.5194/amt-10-979-2017 ◽

2017 ◽

Vol 10 (3) ◽

pp. 979-987 ◽

Cited By ~ 9

Author(s):

Angelika Klein ◽

Peter Lübcke ◽

Nicole Bobrowski ◽

Jonas Kuhn ◽

Ulrich Platt

Keyword(s):

Time Series ◽

Wind Direction ◽

Column Density ◽

Image Plane ◽

Propagation Direction ◽

Volcanic Plume ◽

High Temporal Resolution ◽

Good Precision ◽

So2 Flux ◽

Flux Measurements

Abstract. SO2 cameras are becoming an established tool for measuring sulfur dioxide (SO2) fluxes in volcanic plumes with good precision and high temporal resolution. The primary result of SO2 camera measurements are time series of two-dimensional SO2 column density distributions (i.e. SO2 column density images). However, it is frequently overlooked that, in order to determine the correct SO2 fluxes, not only the SO2 column density, but also the distance between the camera and the volcanic plume, has to be precisely known. This is because cameras only measure angular extents of objects while flux measurements require knowledge of the spatial plume extent. The distance to the plume may vary within the image array (i.e. the field of view of the SO2 camera) since the plume propagation direction (i.e. the wind direction) might not be parallel to the image plane of the SO2 camera. If the wind direction and thus the camera–plume distance are not well known, this error propagates into the determined SO2 fluxes and can cause errors exceeding 50 %. This is a source of error which is independent of the frequently quoted (approximate) compensation of apparently higher SO2 column densities and apparently lower plume propagation velocities at non-perpendicular plume observation angles.Here, we propose a new method to estimate the propagation direction of the volcanic plume directly from SO2 camera image time series by analysing apparent flux gradients along the image plane. From the plume propagation direction and the known location of the SO2 source (i.e. volcanic vent) and camera position, the camera–plume distance can be determined. Besides being able to determine the plume propagation direction and thus the wind direction in the plume region directly from SO2 camera images, we additionally found that it is possible to detect changes of the propagation direction at a time resolution of the order of minutes. In addition to theoretical studies we applied our method to SO2 flux measurements at Mt Etna and demonstrate that we obtain considerably more precise (up to a factor of 2 error reduction) SO2 fluxes. We conclude that studies on SO2 flux variability become more reliable by excluding the possible influences of propagation direction variations.

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Characterisation of the magmatic signature in gas emissions from Turrialba Volcano, Costa Rica