The first section of this work examines melt inclusions in phenocrysts from Volcán Popocatépetl and Volcán de Colima within the Trans Mexican Volcanic Belt (TMVB). These inclusions are dacitic to rhyolitic. Trends in melt inclusion major element and water concentrations form the evolved extension of other Mexican volcanics including those presumably derived directly from primitive melts. Water concentrations in Popocatépetl and Colima melt inclusions are similar (0.3 to 3.4 weight percent Hsub2O). Melt-vapor equilibration pressures calculated from dissolved Hsub2O and COsub2 (Popocatépetl) or Hsub2O (Colima) in melt inclusions correspond to depths of entrapment of 12 km or less. Water and carbon dioxide concentrations correlate negatively with SiOsub2 and potassium. Normalized olivine-augite-quartz compositions are consistent with near cotectic crystallization under vapor-saturated conditions at pressures of 1.5 kb or less. Our results show that Popocatépetl and Colima magmas have undergone vapor-saturated crystallization during ascent in conjunction with varying degrees of mixing between degassed rhyo-dacitic and less degassed, mafic melts in the upper portions of the crust. These data suggest melt evolution occurred in conduits or inter-fingered dikes rather than a large stratified magma chamber. Part II looks at the Masaya caldera in Nicaragua. This volcano has erupted frequently in recorded history, producing lava lakes and very high gas emissions. Melt inclusions from Masaya are basaltic, with low Hsub2O (below 0.5 wt. %), low S (less than 300 ppm) and high COsub2 concentrations (up to approximately 6000 ppm). Relationships between water, sulfur, Cl and F in combination with Masaya's high COsub2 and Ba/Zr and Ba/Nb ratios suggest that Masaya has undergone a multi stage degassing process involving 1) shallow degassing, 2) recycling of magma into a deeper reservoir, and 3) fluxing of previously degassed magma with a nearly pure COsub2 vapor. Trace element signatures of melt inclusions are consistent with contributions that have been variably metasomatized by fluids generated by dehydration of subducted sediments and/or altered oceanic crust.

Volatile trace metals are variably enriched in volcanic gases. Metal concentrations in sub-aerially erupted magmas are also depleted in many of these metals. The causes of variable metal enrichment in volcanic gasses, however, remain enigmatic. The objective of this work is to place experimental constraints on kinetic and thermodynamic factors that influence the concentrations of trace metals in volcanic gases. To measure metal mobility in silicate melts, Pt crucibles packed with metal doped glasses of broadly basaltic composition were equilibrated with air and mixed gases at atmospheric pressure. The metals in the melt diffused to the gas/melt interface where they were released as a volatile species. The experiments produced concentration-distance profiles from which diffusivity was derived. Experiments were also conducted in a piston-cylinder apparatus at 1 GPa pressure. In these experiments, melts were equilibrated with Cl-bearing fluids at high temperature and pressure. At equilibrium, trace metals partitioned between the melt and fluid phase as a function of temperature and fluid composition. The diffusivity of Re in melts of natural basalt, andesite and a synthetic composition in the CaO-MgO-Al2O3-SiO2 (CMAS) system has been investigated at 0.1 MPa and 1250-1350C over a range of fO2 conditions from log fO2 = -10 to –0.68. Re diffusivity in natural basalt at 1300C in air is logDRe = -7.2  0.3 cm2/sec and increases to logDRe = -6.6 0.3 cm2/sec when trace amounts of Cl were added to the starting material. At fO2 conditions below the nickel-nickel oxide (NNO) buffer Re diffusivity decreases to logDRereducing = -7.60.2 cm2/sec and to logDReandesite = -8.4  0.2 cm2/sec in andesite melt. Cd, Re, Tl, Pb, Sb and Te diffusivity in CMAS and Na2O-MgO-Al2O3-SiO2 (NMAS) melts were also determined at 0.1 MPa and 1200-1350C. In the CMAS composition at 1300C, the fastest diffusing element was Cd having a logDCd = -6.5  0.2. The slowest element was Re with logDRe = -7.5  0.3. Diffusivities of Sb, Te, Pb and Tl have intermediate values where logDSb = -7.1  0.1, logDTe = -7.2  0.3, logDPb = -7.1  0.2, logDTl = -7.0  0.2 cm2/sec. In the NMAS composition, logDRe = -6.5  0.2, logDSb = -6.0  0.2, logDPb = -6.1  0.1, logDTl = -5.8  0.2 cm2/sec. Fluid/melt partition coefficients ( ) of Re, Mo, W, Tl and Pb between fluid (H2O + Cl) and a haplobasaltic melt in the CMAS system were measured between 1200 and 1400°C at 1 GPa and fluid chlorine molarities from 7.7 to 27 mol/L. At 1300°C and fluid molarity of 7.7 mol/L, = 9.8±1.8, = 11.8±1.6, = 3.7±1.6, = 4.5±1.4 and = 2.4 ±1.8. Both Mo and Re were shown to partition most strongly into the fluid at all temperatures and fluid chlorinities. Differences in diffusivity of volatile heavy metal ions to a lead to significant fractionation between these metals in magmas during degassing. Given the observed differences in Cd and Re diffusivities, an increase in the normalized Cd/Re ratio in the gas phase with increasing bubble growth rate is predicted. Monitoring of the Cd/Re ratios in aerosols from degassing volcanoes may provide a tool for predicting volcanic eruption. Modeling of Re using the values measured here support the contention that subaerial degassing is the cause of lower Re concentrations in arc-type and ocean island basalts compared to mid-ocean ridge basalts. The model results were also compared with emanation coefficients for trace metals from natural volcanoes. The magnitudes of the modeled Re/Tl and Re/Pb in fluids at 1300C and the lowest fluid chlorinities were less than that observed from their emanation coefficients. Re and Pb are more sensitive to fluid chlorinity than Tl. The ratios of Re/Tl and Re/Pb expected from emanation coefficients are closely matched if partitioning values for experiments having fluid chlorinities of ~16-20 MCl at 1300C are used.

Volatile trace metals are variably enriched in volcanic gases. Metal concentrations in sub-aerially erupted magmas are also depleted in many of these metals. The causes of variable metal enrichment in volcanic gasses, however, remain enigmatic. The objective of this work is to place experimental constraints on kinetic and thermodynamic factors that influence the concentrations of trace metals in volcanic gases. To measure metal mobility in silicate melts, Pt crucibles packed with metal doped glasses of broadly basaltic composition were equilibrated with air and mixed gases at atmospheric pressure. The metals in the melt diffused to the gas/melt interface where they were released as a volatile species. The experiments produced concentration-distance profiles from which diffusivity was derived. Experiments were also conducted in a piston-cylinder apparatus at 1 GPa pressure. In these experiments, melts were equilibrated with Cl-bearing fluids at high temperature and pressure. At equilibrium, trace metals partitioned between the melt and fluid phase as a function of temperature and fluid composition. The diffusivity of Re in melts of natural basalt, andesite and a synthetic composition in the CaO-MgO-Al2O3-SiO2 (CMAS) system has been investigated at 0.1 MPa and 1250-1350C over a range of fO2 conditions from log fO2 = -10 to –0.68. Re diffusivity in natural basalt at 1300C in air is logDRe = -7.2  0.3 cm2/sec and increases to logDRe = -6.6 0.3 cm2/sec when trace amounts of Cl were added to the starting material. At fO2 conditions below the nickel-nickel oxide (NNO) buffer Re diffusivity decreases to logDRereducing = -7.60.2 cm2/sec and to logDReandesite = -8.4  0.2 cm2/sec in andesite melt. Cd, Re, Tl, Pb, Sb and Te diffusivity in CMAS and Na2O-MgO-Al2O3-SiO2 (NMAS) melts were also determined at 0.1 MPa and 1200-1350C. In the CMAS composition at 1300C, the fastest diffusing element was Cd having a logDCd = -6.5  0.2. The slowest element was Re with logDRe = -7.5  0.3. Diffusivities of Sb, Te, Pb and Tl have intermediate values where logDSb = -7.1  0.1, logDTe = -7.2  0.3, logDPb = -7.1  0.2, logDTl = -7.0  0.2 cm2/sec. In the NMAS composition, logDRe = -6.5  0.2, logDSb = -6.0  0.2, logDPb = -6.1  0.1, logDTl = -5.8  0.2 cm2/sec. Fluid/melt partition coefficients ( ) of Re, Mo, W, Tl and Pb between fluid (H2O + Cl) and a haplobasaltic melt in the CMAS system were measured between 1200 and 1400°C at 1 GPa and fluid chlorine molarities from 7.7 to 27 mol/L. At 1300°C and fluid molarity of 7.7 mol/L, = 9.8±1.8, = 11.8±1.6, = 3.7±1.6, = 4.5±1.4 and = 2.4 ±1.8. Both Mo and Re were shown to partition most strongly into the fluid at all temperatures and fluid chlorinities. Differences in diffusivity of volatile heavy metal ions to a lead to significant fractionation between these metals in magmas during degassing. Given the observed differences in Cd and Re diffusivities, an increase in the normalized Cd/Re ratio in the gas phase with increasing bubble growth rate is predicted. Monitoring of the Cd/Re ratios in aerosols from degassing volcanoes may provide a tool for predicting volcanic eruption. Modeling of Re using the values measured here support the contention that subaerial degassing is the cause of lower Re concentrations in arc-type and ocean island basalts compared to mid-ocean ridge basalts. The model results were also compared with emanation coefficients for trace metals from natural volcanoes. The magnitudes of the modeled Re/Tl and Re/Pb in fluids at 1300C and the lowest fluid chlorinities were less than that observed from their emanation coefficients. Re and Pb are more sensitive to fluid chlorinity than Tl. The ratios of Re/Tl and Re/Pb expected from emanation coefficients are closely matched if partitioning values for experiments having fluid chlorinities of ~16-20 MCl at 1300C are used.

abstract: Among volcanic gases, sulfur dioxide (SO2) is by far the most commonly measured. More than a monitoring proxy for volcanic degassing, SO2 has the potential to alter climate patterns. Persistently active explosive volcanoes are characterized by short explosive bursts, which often occur at periodic intervals numerous times per day, spanning years to decades. SO2 emissions at those volcanoes are poorly constrained, in large part because the current satellite monitoring techniques are unable to detect or quantify plumes of low concentration in the troposphere. Eruption plumes also often show high concentrations of ash and/or aerosols, which further inhibit the detection methods. In this work I focus on quantifying volcanic gas emissions at persistently active explosive volcanoes and their variations over short timescales (minutes to hours), in order to document their contribution to natural SO2 flux as well as investigate the physical processes that control their behavior. In order to make these measurements, I first develop and assemble a UV ground-based instrument, and validate it against an independently measured source of SO2 at a coal-burning power plant in Arizona. I establish a measurement protocol and demonstrate that the instrument measures SO2 fluxes with < 20 % error. Using the same protocol, I establish a record of the degassing patterns at Semeru volcano (Indonesia), a volcano that has been producing cycles of repeated explosions with periods of minutes to hours for the past several decades. Semeru produces an average of 21-71 tons of SO2 per day, amounting to a yearly output of 8-26 Mt. Using the Semeru data, along with a 1-D transient numerical model of magma ascent, I test the validity of a model in which a viscous plug at the top of the conduit produces cycles of eruption and gas release. I find that it can be a valid hypothesis to explain the observed patterns of degassing at Semeru. Periodic behavior in such a system occurs for a very narrow range of conditions, for which the mass balance between magma flux and open-system gas escape repeatedly generates a viscous plug, pressurizes the magma beneath the plug, and then explosively disrupts it. / Dissertation/Thesis / Doctoral Dissertation Geological Sciences 2015

Volatile heavy metals are liberated from magmas during eruptive and passively degassing volcanic activity. Volcanic emanations have been estimated to contribute 20-40% of volatile elements such as Bi, Pb, As or Sb, and up to 40-50 % of Cd and Hg annually (Nriagu, 1989). Some workers, however, believe these ranges are too high (Hinkley, 1999) or too low (Zreda-Gostynska and Kyle, 1997) leading to considerable differences in global inventory budgets of these metals and the degree to which they load the atmosphere. The objective of this work is to investigate the behavior of volatile heavy metals such as Au, Tl, As, Pb etc. in subaerially erupted magmas and experimentally in silicate melts. Analysis of natural pumice samples confirm the futile, sporadic nature of Hg and associated heavy metals, suggesting these metals are fully degassed prior to deposition. Diffusion experiments were conducted in natural basalt, dacite and synthetic rhyolite (Ab-Or-Qz minimum eutectic) over a range of temperatures (1200 – 1430 °C) at 0.1 MPa. Starting compositions were doped with a heavy metal cocktail (Bi, Pb, Tl, Au, Re, Sb, Sn, Cd, Mo, As, Cu) and loaded into open top Pt capsules. One set of experiments examined the effect of melt composition (polymerization) on element diffusion, and the second investigated the effects of ligands on diffusion by adding known concentrations of Cl and S. During experiments of varying duration, concentration gradients arose in the volatile trace metals due to their varying volatility, as measured (normal to the melt/gas interface) by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) in quenched glasses. Diffusion profiles followed an Arrhenius relationship from which diffusion coefficients (D) and activation energies (Ea) were obtained for Au, Tl, As, Cd, Re, Pb and Bi (in decreasing order of volatility). Results show Au and Tl are the most volatile in dacite and rhyolite yielding LogDDac Au = -10.7 ± 0.1 m2/s and LogDDac Tl = -10.9 ± 0.1 m2/s in dacite, and LogDRhy Au = -10.9 ± 0.1 m2/s and LogDRhy Tl = -11.3 ± 0.3 m2/s in rhyolite respectively. The D for Au could not be measured in basalt but Tl was the fastest diffusing species LogDBas Tl = -10.8 ± 0.2 m2/s. Ligands Cl and S were shown to increase the volatilities of all metals, with S having a more profound effect. Diffusivities were applied to a simple 1D bubble growth model (Smith 1955). Model results indicate diffusion coefficients play a major role in metal fractionation processes occurring at depths that ultimately dictate what metal ratios are measured at the surface of volcanoes.

Sulfur dioxide (SO2) is a gas typical of high temperature magmatic degassing, being its<p>third most abundant constituent after water vapor and carbon dioxide. SO2 flux measurements<p>are used to characterized and monitor volcanic degassing. This thesis presents advanced<p>methods for measuring the SO2 emitted in the troposphere by passive degassing volcanoes.<p>These methods are based on the absorption of infrared (IR) and ultraviolet (UV) light by SO2<p>molecules. They make use of the data acquired by satellite borne sensors (ASTER, OMI and<p>MODIS), and collected in the field using a UV camera equipped with filters<p>ASTER is a multispectral sensor observing the Earth in the thermal IR with a 90 m<p>ground resolution. The developed retrieval algorithm works with band ratios<p>(B10+B12)/2B11 and B14/B11, to avoid spectral interference from other variables than SO2.<p>With this algorithm, the impact of interferers such as atmospheric water vapor, sulfate<p>aerosols and ground emissivity is minimal, as demonstrated by radiative transfer simulations<p>by applying of the algorithm to real ASTER images and by comparing the results with ground<p>based data. ASTER is a kind of unifying thread for this thesis because its high ground<p>resolution fills the gap existing between highly localized ground based SO2 measurements and<p>the global coverage of other satellites with coarser pixels such as OMI and MODIS.<p>OMI is an imaging spectrometer operating in the UV, with a daily global coverage, a<p>high sensitivity to SO2 and a ground resolution of 13x24km. The OMI-ASTER comparison<p>shows that the SO2 columns measured on OMI pixels are two orders of magnitude smaller<p>than those of ASTER, because of the huge difference in the pixel size of the two satellites.<p>The flux measurements however are generally in good agreement. The analysis of a large<p>number of images shows that ASTER is better for cloud free scenes while OMI has an<p>optimal signal to noise ratio when the plume is lying above a low cloud cover. A practical<p>detection limit for SO2 flux measurements in tropospheric plumes has also been established:<p>5kg/s.<p>The comparison between ASTER measurements of SO2 column amounts with those of<p>MODIS (a multispectral IR imager with 1km ground resolution) shed light on systematic<p>errors in MODIS measurements. These errors were quantified and their origins were separated<p>and identified. This work demonstrates the limitations of MODIS for SO2 measurements.<p>A UV camera equipped with filters has also been developed to achieve 2D SO2 from the<p>ground at a high spatial and temporal resolution. The potential provided by this new type of<p>instruments has been demonstrated during a field campaign on Turrialba Volcano (Costa<p>Rica). The integration of measurements obtained using the camera, ASTER and OMI revealed<p>a high and sustained SO2 flux, which can be explained only by the degassing of a recently<p>intruded magma body. The slow decrease of SO2 flux since January 2010 suggests a<p>progressive exhaustion of the volatile content of the magma.<p>Finally, we applied the band ratio algorithm to a series of ASTER images of the recent<p>eruption of Eyjafjallajökull in April-May 2010. The SO2 measurements provide interesting<p>insights into the complex eruptive dynamics and into the control of hydromagmatic<p>interactions on eruptive gas release into the atmosphere. /<p><p>Le dioxyde de soufre (SO2) est un gaz typique du dégazage magmatique de haute<p>température, dont il est le troisième composant le plus abondant derrière H2O et CO2. Le flux<p>de SO2 est un excellent paramètre pour caractériser le dégazage volcanique et surveiller son<p>évolution dans le temps. Cette thèse présente de nouvelles méthodes de mesures des flux de<p>SO2 émis par l’activité volcanique. Ces méthodes se basent sur l’absorption de la molécule de<p>SO2 dans l’infrarouge (IR) et l’ultraviolet (UV). Elles utilisent les données prises par des<p>senseurs embarqués sur des satellites (ASTER, OMI et MODIS) ou opérés depuis le sol<p>(caméra UV munie de filtres).<p>Le senseur ASTER opère dans l’IR thermique avec une résolution spatiale de 90 m par<p>pixel. L’algorithme de mesure développé pour ce satellite n’est sensible qu’à la concentration<p>en SO2 et pratiquement pas aux paramètres interférents qui posaient problèmes aux méthodes<p>existantes :la vapeur d’eau atmosphérique, les aérosols de sulfate dans le panache et<p>l’émissivité de la surface sous-jacente. ASTER est un peu le fil conducteur de cette thèse, car<p>sa haute résolution spatiale lui permet de faire le lien entre des mesures au sol et les mesures<p>faites par d’autres satellites comme OMI et MODIS.<p>Le satellite OMI est un spectromètre imageant qui opère dans l’UV, avec une<p>couverture globale journalière, une haute sensitivité au SO2 et une résolution spatiale de<p>13x24km. La comparaison OMI-ASTER montre que les colonnes mesurées sur les pixels<p>d’OMI sont de deux ordres de grandeur inférieurs à celles d’ASTER, à cause de la différence<p>de résolution spatiale entre les deux satellites. Les mesures de flux, par contre, montrent une<p>très bonne concordance. L’analyse d’un grand nombre d’images a permis d’établir qu’ASTER<p>est meilleur pour des scènes sans nuages tandis qu’OMI est meilleur quand une couverture<p>nuageuse présente sous le panache augmente son rapport signal sur bruit. Une limite de<p>détection pratique a aussi été établie pour les flux de SO2 dans les panaches volcaniques dans<p>la basse troposphère :5kg/s.<p>La comparaison des mesures d’ASTER avec celle de MODIS a permis de démontrer les<p>limites de MODIS pour la mesure du SO2. Des erreurs systématiques sur les mesures de<p>MODIS on été mises en évidence et quantifiées. Ces erreurs sont dues aux interférents<p>spectraux que sont la vapeur d’eau atmosphérique et les aérosols sulfatés. L’émissivité est<p>aussi un important facteur d’erreur pour MODIS.<p>Une caméra UV équipée d’un système de filtres a également été développée pour<p>mesurer le SO2 en 2D, à haute résolution spatiale et temporelle. Le potentiel offert par ce<p>nouveau type d’instrument a été démontré lors d’une campagne de mesures sur le volcan<p>Turrialba (Costa Rica). La combinaison de mesures de SO2 réalisée avec la caméra, ASTER<p>et OMI a permis de mettre en évidence des flux très élevés (30-50kg/s) qui ne peuvent<p>s’expliquer que par une intrusion récente de magma juvénile en cours de dégazage.<p>Enfin, les mesures de SO2 ont réalisées à partir des images ASTER pendant l’éruption<p>du volcan Eyjafjallajökull en avril-mai 2010. Ces mesures fournissent des informations<p>intéressantes sur les dynamismes éruptifs qui se sont succédé et sur le contrôle des émissions<p>de SO2 dans l’atmosphère par les interactions magma-eau. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished