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

<p>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.</p>

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

<p>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.</p>

Fluids composition in the mantle beneath the Eastern Transylvanian Basin inferred from mineral chemistry and noble gases in fluid inclusions of ultramafic xenoliths

&lt;p&gt;The investigation of noble gases (He, Ne, Ar) and CO&lt;sub&gt;2&lt;/sub&gt; in fluid inclusions (FI) of mantle-derived rocks from the Sub Continental Lithospheric Mantle (SCLM) is crucial for constraining its geochemical features and evolution as well as the volatiles cycle, and for better evaluating the information arising from the study and monitoring of volcanic and geothermal gases. Eastern Transylvanian Basin in Romania is one of the places in Central-Eastern Europe where mantle xenoliths are brought to the surface by alkaline magmatism, offering the opportunity for applying the above-mentioned approach. Moreover, this locality is one of the few places on Earth where alkaline eruptions occurred contemporaneously with calc-alkaline activity, thus being a promising area for the investigation of subduction influence on the magma sources and volatiles composition.&lt;/p&gt;&lt;p&gt;In this work, we studied petrography, mineral chemistry and noble gases in FI of mantle xenoliths found in Per&amp;#351;ani Mts. alkaline volcanic products. Our findings reveal that the local mantle recorded two main events. The first was a pervasive, complete re-fertilization of a previously depleted mantle by a calc-alkaline subduction-related melt, causing the formation of very fertile, amphibole-bearing lithotypes. Fluids involved in this process and trapped in olivine, opx and cpx, show &lt;sup&gt;4&lt;/sup&gt;He/&lt;sup&gt;40&lt;/sup&gt;Ar* ratios up to 1.2 and among the most radiogenic &lt;sup&gt;3&lt;/sup&gt;He/&lt;sup&gt;4&lt;/sup&gt;He values of the European mantle (5.8 &amp;#177; 0.2 Ra), reflecting the recycling of crustal material in the local lithosphere. The second event is related to a later interaction with an alkaline metasomatic agent similar to the host basalts, that caused slight LREE enrichment in pyroxenes and crystallization of disseminated amphiboles, with FI showing &lt;sup&gt;4&lt;/sup&gt;He/&lt;sup&gt;40&lt;/sup&gt;Ar* and &lt;sup&gt;3&lt;/sup&gt;He/&lt;sup&gt;4&lt;/sup&gt;He values up to 2.5 and 6.6 Ra, respectively, more typical of magmatic fluids.&lt;/p&gt;&lt;p&gt;Although volcanic activity in the Per&amp;#351;ani Mts. is now extinct, strong CO&lt;sub&gt;2&lt;/sub&gt; degassing (8.7 &amp;#215; 10&lt;sup&gt;3&lt;/sup&gt; t/y) in the neighbouring Ciomadul volcanic area may indicate that magma is still present at depth (Kis et al., 2017; Laumonier et al., 2019). The gas manifestations present from Ciomadul area are the closest to the outcrops containing mantle xenoliths for comparison of the noble gas composition in FI. &lt;sup&gt;3&lt;/sup&gt;He/&lt;sup&gt;4&lt;/sup&gt;He values from Stinky Cave (Puturosul), Dobo&amp;#351;eni and Balvanyos are up to 3.2, 4.4 and 4.5 Ra, respectively, indicating the presence of a cooling magma (Vaselli et al., 2002 and references therein). In the same area and more recently, Kis et al. (2019) measured &lt;sup&gt;3&lt;/sup&gt;He/&lt;sup&gt;4&lt;/sup&gt;He ratios up to 3.1 Ra, arguing that these values indicate a mantle lithosphere strongly contaminated by subduction-related fluids and post-metasomatic ingrowth of radiogenic &lt;sup&gt;4&lt;/sup&gt;He. Our findings consider more likely that magmatic gases from Ciomadul volcano are not representative of the local mantle but are being released from a cooling and aging magma that resides within the crust. Alternatively, crustal fluids contaminate magmatic gases while they are rising to the surface.&lt;/p&gt;&lt;p&gt;&amp;#160;&lt;/p&gt;&lt;p&gt;Kis et al. (2017). Journal of Volcanology and Geothermal Research 341, 119&amp;#8211;130.&lt;/p&gt;&lt;p&gt;Kis et al. (2019) Geochem. Geophys. Geosyst. 20, 3019-3043.&lt;/p&gt;&lt;p&gt;Laumonier et al. (2019) Earth and Planetary Science Letters, 521, 79-90.&lt;/p&gt;&lt;p&gt;Vaselli et al. (2002) Chemical Geology 182, 637&amp;#8211;654.&lt;/p&gt;

Volatile metal emissions from volcanic degassing and lava-seawater interactions at Kīlauea Volcano, Hawai’i

Volcanoes represent one of the largest natural sources of metals to Earth’s surface. Emissions of these pollutants and/or nutrients have important implications for the biosphere. We compare gas and particulate chemistry, including metals, of the substantial magmatic (≥200 kt/day SO2) and lava-seawater interaction (laze) plumes from the 2018 eruption of Kīlauea, Hawai’i. The magmatic plume contains abundant volatile chalcophile metals (e.g. Se), whereas the laze is enriched in seawater components (e.g. Cl), yet Cu concentrations are 105 times higher than seawater. High-temperature speciation modelling of magmatic gases at the lava-air interface emphasises chloride’s critical role in metal/metalloid complexation during degassing. In the laze, concentrations of moderately (Cu, Zn, Ag) to highly volatile (Bi, Cd) metals are elevated above seawater. These metals have an affinity for chloride and are derived from late-stage degassing of distal lavas, potentially facilitated by the HCl gas formed as seawater boils. Understanding these processes yields insights into the environmental impacts of volcanism in the present day and geological past.

Thermodynamic model of chemical re-magnetization on the example of Girvas paleovolcano of the Onega structure of Karelian craton

Volcano Girvas is a complexly constructed volcano complex of the Yatuli age. Apparently, it is a shield lava volcano, which was probably one of the supply channels of the vast lava field of the western Prionezhie region within the Girvas volcanic zone. Despite the fact that the Girvassky volcano is bare only fragmentary, the structure of the current is perfectly preserved in the rocks, allowing to reconstruct the direction of flow. Among these rocks, there is a zone of postvolcanic hydrothermal changes in the rocks, consisting mainly of nesting and veined tourmalization and silicification, as well as subsequent epidotization, sulfidization, chloritization and albitization. The zones of secondary changes are confined to faults, while their spatial-temporal correlation remains unclear. Reconstruction of the geological structure showed that there were two main processes at the Girvasa volcano: 1) pneumatolysis of type due to magmatic gases separated from gabbro-dolerite sills, 2) heating and circulation of exogenous waters with formation of near propylites. Based on the proposed scheme, thermodynamic modeling was performed.

MINERALOGY AND GEOCHEMISTRY OF THE TRIADESGALANA PB-ZN-AG-AU INTERMEDIATE-HIGH SULFIDATION EPITHERMAL MINERALIZATION, MILOS ISLAND, GREECE

The Triades-Galana Pb-Zn-Ag-Au mineralization is a shallow-submarine epithermal mineralization located along NE-trending faults, NW Milos Island, Greece. It is hosted in 2.5–1.4 Ma pyroclastic rocks and is genetically related to andesitic/dacitic lava domes. Mineralization occurs as breccias, quartz-barite galena veins and stockworks within sericite-adularia or kaolinitic altered rocks. The mineralization is enriched in Mo, W and base- and precious metals (e.g. Pb, Zn, Ag) similarly to the neighbouring mineralization at Kondaros-Katsimouti and Vani, indicating common source of metals from a deep buried granitoid feeding western Milos with metals and volatiles. Paragenetic relations suggest early deposition of pyrite, followed by famatinite, polybasite and Ag-rich tetrahedrite, and then by enargite, suggesting fluctuating sulfidation states during ore formation. The evolution from Sb- towards As-rich enrichment indicate a renewed magmatic pulse (probably in the form of magmatic gases) in the hydrothermal system. Silver is present in the structure of sulfosalts (up to 66.2 wt.% in polybasite-pearceite, 15.1 wt.% in tetrahedrite and 60 wt. % in pyrargyrite). Boiling processes (as evidenced by the presence of adularia accompanying intermediate-sulfidation ore) and mixing with seawater (presence of hypogene lead chlorides) and contemporaneous uplift, contributed to ore formation.

Multi-parametric investigation of the volcano-hydrothermal system at Tatun Volcano Group, Northern Taiwan

The Tatun Volcano Group (TVG) is located in northern Taiwan near the capital Taipei. In this study we selected and analyzed almost four years (2004–2007) of its seismic activity. The seismic network established around TVG initially consisted of eight three-component seismic stations with this number increasing to twelve by 2007. Local seismicity mainly involved high frequency (HF) earthquakes occurring as isolated events or as part of spasmodic bursts. Mixed and low frequency (LF) events were observed during the same period but more rarely. During the analysis we estimated duration magnitudes for the HF earthquakes and used a probabilistic non-linear method to accurately locate all these events. The complex frequencies of LF events were also analyzed with the Sompi method indicating fluid compositions consistent with a misty or dusty gas. We juxtaposed these results with geochemical/temperature anomalies extracted from fumarole gas and rainfall levels covering a similar period. This comparison is interpreted in the context of a model proposed earlier for the volcano-hydrothermal system of TVG where fluids and magmatic gases ascend from a magma body that lies at around 7–8 km depth. Most HF earthquakes occur as a response to stresses induced by fluid circulation within a dense network of cracks pervading the upper crust at TVG. The largest (ML ~ 3.1) HF event that occurred on 24 April 2006 at a depth of 5–6 km had source characteristics compatible with that of a tensile crack. It was followed by an enrichment in magmatic components of the fumarole gases as well as a fumarole temperature increase, and provides evidence for ascending fluids from a magma body into the shallow hydrothermal system. This detailed analysis and previous physical volcanology observations at TVG suggest that the region is volcanically active and that measures to mitigate potential hazards have to be considered by the local authorities.