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

Ce manuscrit présente les premiers résultats d'études élémentaires et isotopiques du Zn, du Sr et du Pb, réalisées dans les principaux types d'échantillons liés aux gaz volcaniques (gaz, sublimés, eaux thermales, roches), ainsi que deux nouvelles méthodologies d'échantillonnage des émanations volcaniques. Les variations isotopiques du Zn observées au Merapi suggèrent que les processus de changement de phase (fluides/solides) peuvent provoquer des fractionnements isotopiques significatifs des éléments trace métalliques. L'étude couplée Sr/Pb réalisée à Vulcano indique que les compositions en éléments trace métalliques des fumerolles et des eaux thermales sont influencées par les sources naturelles et anthropiques. Ce travail a aussi permis la mise au point de nouvelles méthodologies d'échantillonnage et d'analyse des gaz et des panaches volcaniques, permettant d'accéder à la composition chimique complète de ces manifestations gazeuses de manière simple et efficace.

L'axe principal de cette thèse est la caractérisation des processus de dégazage magmatique des éléments traces, du soufre et des halogènes de deux volcans actifs : Hekla (Islande) et Masaya (Nicaragua). <br />Une étude sur les inclusions magmatiques (MIs) a permis de suivre l'évolution des volatils dissous dans le système volcanique d'Hekla au cours de la différenciation magmatique (cristallisation fractionnée). Ceci a permis d'estimer les concentrations en volatils dissous "attendues" dans le liquide pré-éruptif. Cette approche permet donc de ne pas sous-estimer les concentrations des liquides piégés dans les MIs et améliore ainsi les contraintes sur la masse de volatils émise dans l'atmosphère. Cette étude indique que, lors de l'éruption de février 2000, Hekla a émis dans l'atmosphère 0.1 Mt de HCl, 0.2 Mt de HF et 3.8 Mt de SO2. La chimie de la phase sub-Plinienne de cette éruption a été étudiée, de façon plus approfondie, grâce aux averses neigeuses qui ont traversé le panache volcanique. L'étude de ces neiges a montré que l'enrichissement des éléments volatils est lié à un processus de dégazage sous forme de chlorures, fluorures et sulfates. En revanche, l'enrichissement des éléments réfractaires est expliqué par un processus de dissolution non-stoechiométrique des téphras par la phase gazeuse riche en fluor au sein du panache éruptif.<br />Une étude basée sur les MIs a permis de confirmer la théorie de Walker et al. (1993) selon laquelle la différenciation des magmas tholéiitiques du Masaya se produit à basse pression à partir d'un magma relativement "sec" de composition homogène dans le temps. La caractérisation physico-chimique des aérosols par MEB et la chimie de la phase éruptive du volcan Masaya suggèrent que la plupart des éléments traces sont dégazés sous forme de chlorures, mais aussi sous forme de sulfates et chloro-sulfates. De plus, la quantification des flux de matière a montré que le dégazage au Masaya est une source importante de pollution atmosphérique.

This study shows how the composition of gases released from a single magmatic source may be modified during their ascending path. The main processes that influence the composition of the gases in these high temperature fumarolic environments, are: 1) interactions with wallrocks during gas ascent, which change the fugacities of the metal volatile species and affect the equilibrium between major species (fH2S/fSO2; fH2/fH2O); 2) mixing with meteoric water with consequent Cl adsorption, which may account for the Cl depletion of the gases; 3) remobilisation of previously formed sublimates and/or incrustation deposits. Comparison between the thermochemical models and the mineralogical composition of the silica tubes at Kudryavy and Satsuma-Iwojima volcanoes suggests that high fO2 due to the mixing of the gases with air during their injection into the atmosphere significantly reduces the volatility of several trace elements (As, Sb, Sn, Na, K, Tl, Te, Se and Cd). Comparisons between the enriched metals in aerosols and in the gases suggest that Mo, Pb, Bi, Na, K, Cu, Zn or Fe, which are enriched in the gases, are preferentially deposited in the gas conduits and vents whereas the highly volatile metals (Te, Tl, Sb, As and Se) and Cd condense in the plume.<p>This study determines the reactions that may occur during the alteration of rocks in high temperature fumarolic environments. Three different processes of alteration prevail: <p>(1) Acidic alteration which is characterized by the complete absence of clays, because the constant supply of gases to these systems allows for the pH values of the acidic fluids to be maintained low enough to prevent the precipitation of clay minerals. Complete leaching of all cations, except Si, from the primary silicates leads to important "silicification" of the wall rock. The primary mineral cations are leached in the following order: K, Na > Ca > Fe, Mg > Al > Si, Ti. The fluids enriched in these cations circulate in microcracks at different temperatures and different redox conditions and lead to the precipitation of secondary incrustations. At Kudryavy the incrustations are mainly sulfates. At Usu the lower sulfur/fluoride ratio of the gases allows the occurrence of aluminum fluoride incrustations. The order of primary minerals dissolution (olivine > plagioclase > pyroxene > matrix glass > Fe-Ti oxides) is established for both sites studied. <p>(2) Alteration by an oxidized volcanic gas, resulting from mixing with the atmosphere (500 to 300°C). At Kudryavy, thermochemical modeling suggests that anhydrite and anhydrous sulfates, which occur at intermediate temperatures, are formed by interactions of the rock with oxidized gas. <p>(3) The most important outcome of this work is the identification of the features of alteration by the volcanic gas that directly reacts with the rock at high temperatures (T > 500°C). The Kudryavy rocks show evidences for mineral transformations, which occur in the presence of the volcanic gas phase. Volcanic gas directly reacts with rocks at high temperatures (T > 500°C). The gas destabilizes the primary minerals, remobilizes the rock-bearing cations, and leads to the formation of second mineral assemblages. These transformations occur in situ, without significant mobility (gain or loss) of the cations. The high temperature secondary associations are characterized by the presence of andradite, hedenbergite, hercynite, tridymite/cristobalite. Anhydrite and anhydrous Al sulfate may occur within these mineral assemblages if the gas is oxidized.<p> / Doctorat en sciences, Spécialisation géologie / info:eu-repo/semantics/nonPublished

Surface manifestations of hydrothermal fluids such as fumaroles and hot springs provide valuable information about the level of activity of a volcano during quiescent period. Geochemical study of gas and spring waters is useful to elaborate geochemical model for magmatic-hydrothermal system. Furthermore, temporal geochemical monitoring of these fluids with time provides a better understanding in processes occurring inside the volcano and can be useful to detect any changes in the activity of the magmatic-hydrothermal system. This thesis investigates two hydrothermal systems at Kelud and Papandayan volcanoes that are located at Java Island in Indonesia. Kelud is considered as one of the most dangerous volcanoes of Java because of its frequent eruptions. After the last eruption that occurred in 1990, a new lake rapidly filled the crater of Kelud volcano. Water samples collected since 1993 are near neutral Na-K chloride fluids and are typical of aged hydrothermal system where the acidity has been completely neutralized by fluid-rock interaction and where the emission of acid magmatic gases has stopped. Two sudden increases in lake temperature in 1996 and 2001 were accompanied by rapid changes in lake water compositions and suggest the existence of two hydrothermal systems feeding the lake: a shallow hydrothermal system dominated by Ca-Mg sulfate waters and a deepest aquifer with neutral alkali chloride waters. From 2001 to 2005, measurements of CO2 emitted by the surface of the lake were performed by using the accumulation chamber method modified in order to work at the surface of a crater lake. Two statistical methods were used to process data: the graphical statistical and stochastic simulation methods. The results of graphical statistical approach showed that two different degassing processes are acting at the lake surface: one corresponding to CO2 fluxes resulting from rising bubbles and the other corresponding to equilibrium diffusion of dissolved CO2 at the water-air surface. Total CO2 emission rate estimated by stochastic simulation ranges from 105 t/day for 2001 to 32 t/day for 2005. Thermal energy released by the lake was also estimated by using an energy balance model with a new constraint using the CO2 flux. The thermal flux decreased from 200 MW (2001) to 100 MW (2002) and then remained stable. Correlation between the chemical data of waters, the fluxes of CO2 and energy show that a constant decrease in the level of activity of the volcano since 1993 occurred although the lake temperature has been stable since 2003. Since the last magmatic eruption that occurred in 1772, phreatic eruptions occur on Papandayan volcano with the last one in 2002. The volcanic material ejected during this eruption is essentially made of altered rocks from within the hydrothermal system. The interaction of acid waters with the host rocks corresponds to an advanced argilic alteration. The chemical compositions of waters from Papandayan volcano and Kelud lake waters are contrasting. Indeed, the spring waters sampled since 1994 are acid sulfate-chloride waters and acid sulfate waters. The chemical and isotopic analyses of gases and waters suggest a significant magmatic contribution in SO2, HCl and HF to the hydrothermal system. The chemical composition of waters sampled after the 2002 eruption have provided information about origin of this eruption. Decrease in chloride concentration and in delta 34S of dissolved sulfates showed that the magmatic contribution in these fluids are less important and that the waters are likely to be formed by the condensation of steam (H2O, H2S) rising from a boiling aquifer.

Des observations macroscopiques et microscopiques sur les plantes actuelles et fossiles ont été effectuées. Sur les plantes actuelles ont été effectué des observations relativement aux effets des gaz volcaniques sur l’ultrastructure des cuticules de Pinus halepensis et de Erica arborea récoltés dans l’aire volcanique des Campi Flegrei, Italie. Les observations conduites au TEM sur les cuticules de P. halepensis, influencé et non influencé par les gaz volcaniques, ont montré que : 1) l'épaisseur totale de la CM (cuticule) + CW (paroi pectocellulosique) ne subit pas de variations significatives d'épaisseur ; 2) la cuticule des aiguilles influencée par les gaz volcaniques montre une accumulation d’oxalate de calcium ainsi que 3) un réarrangement des fibrilles disposées parallèlement à la surface. Les observations conduites sur E. arborea ont permis de 1) constater que les épaisseurs totales des cuticules, influencées ou non par les gaz, sont significativement différentes ; 2) en présence de gaz volcaniques la couche externe A2 subit un accroissement d’épaisseur significatif. Par rapport aux macro-restes végétaux fossiles, les localités du Crétacé de Cusano Mutri et Pietraroja ont été étudiées. Le première site fossilifère a permis 1) d’identifier plusieurs taxa appartenant aux conifères; 2) de décrire une nouvelle espèce de conifère: Frenelopsis cusanensis; 3) de trouver l’angiosperme ancestrale Montsechia vidalii. L’étude taxonomique a permis de décrire des entités typiques de la Province Euro-Sinienne. L’étude sédimentologique et systématique montre un climat plutôt tropical-subtropical, des abondants fusains montrant des incendies naturels. / Macroscopical and microscopical observations on extant and fossil plants have been made. Observations on extant plants led to study the effects of volcanic gases on the cuticle ultrastructure of Pinus halepensis and Erica arborea sampled in the volcanic area of Phlegrean Italy. TEM observations on P. halepensis cuticles fumigated or not by volcanic gases revealed: 1) insignificant thickness variations of the cell wall plus cuticle among current- and first-year-old needles of both fumigated and not fumigated trees; 2) a calcium oxalate accumulation in fumigated leaves; 3) moreover, in respect to the cell surface, fibrils are disposed parallel to the surface of the cuticle. In specimens of E. arborea fumigated or not by volcanic gases, 1) the total thickness of cuticles varies significantly; 2) in plants experiencing chronic fumigation the A2 layer increases its thickness. As for fossil plants, the cuticles of Cretaceous Fossil-Lagertätten of Cusano Mutri and Pietraroja have been studied. In the former: 1) numerous taxa belonging to conifers have been identified; 2) the new species Frenelopsis cusanensis has been described; 3) Montsechia vidalii has been found outside of Spain. Taxonomical studies allowed the description of typical Euro-Sinian fossil plants. Sedimentological and taxonomical studies suggest semi-arid or arid conditions in a subtropical or tropical climate. It is worth noting as for Cusano Mutri locality, evidence of wildfire (fusain) suggests a periodic combination of arid periods, high temperatures and lightning strikes.

Surface manifestations of hydrothermal fluids such as fumaroles and hot springs provide valuable information about the level of activity of a volcano during quiescent period. Geochemical study of gas and spring waters is useful to elaborate geochemical model for magmatic-hydrothermal system. Furthermore, temporal geochemical monitoring of these fluids with time provides a better understanding in processes occurring inside the volcano and can be useful to detect any changes in the activity of the magmatic-hydrothermal system. This thesis investigates two hydrothermal systems at Kelud and Papandayan volcanoes that are located at Java Island in Indonesia. Kelud is considered as one of the most dangerous volcanoes of Java because of its frequent eruptions. After the last eruption that occurred in 1990, a new lake rapidly filled the crater of Kelud volcano. Water samples collected since 1993 are near neutral Na-K chloride fluids and are typical of aged hydrothermal system where the acidity has been completely neutralized by fluid-rock interaction and where the emission of acid magmatic gases has stopped. Two sudden increases in lake temperature in 1996 and 2001 were accompanied by rapid changes in lake water compositions and suggest the existence of two hydrothermal systems feeding the lake: a shallow hydrothermal system dominated by Ca-Mg sulfate waters and a deepest aquifer with neutral alkali chloride waters. From 2001 to 2005, measurements of CO2 emitted by the surface of the lake were performed by using the accumulation chamber method modified in order to work at the surface of a crater lake. Two statistical methods were used to process data: the graphical statistical and stochastic simulation methods. The results of graphical statistical approach showed that two different degassing processes are acting at the lake surface: one corresponding to CO2 fluxes resulting from rising bubbles and the other corresponding to equilibrium diffusion of dissolved CO2 at the water-air surface. Total CO2 emission rate estimated by stochastic simulation ranges from 105 t/day for 2001 to 32 t/day for 2005. Thermal energy released by the lake was also estimated by using an energy balance model with a new constraint using the CO2 flux. The thermal flux decreased from 200 MW (2001) to 100 MW (2002) and then remained stable. Correlation between the chemical data of waters, the fluxes of CO2 and energy show that a constant decrease in the level of activity of the volcano since 1993 occurred although the lake temperature has been stable since 2003. Since the last magmatic eruption that occurred in 1772, phreatic eruptions occur on Papandayan volcano with the last one in 2002. The volcanic material ejected during this eruption is essentially made of altered rocks from within the hydrothermal system. The interaction of acid waters with the host rocks corresponds to an advanced argilic alteration. The chemical compositions of waters from Papandayan volcano and Kelud lake waters are contrasting. Indeed, the spring waters sampled since 1994 are acid sulfate-chloride waters and acid sulfate waters. The chemical and isotopic analyses of gases and waters suggest a significant magmatic contribution in SO2, HCl and HF to the hydrothermal system. The chemical composition of waters sampled after the 2002 eruption have provided information about origin of this eruption. Decrease in chloride concentration and in delta 34S of dissolved sulfates showed that the magmatic contribution in these fluids are less important and that the waters are likely to be formed by the condensation of steam (H2O, H2S) rising from a boiling aquifer.<p><p> / Doctorat en sciences, Spécialisation géologie / info:eu-repo/semantics/nonPublished