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>

Geochemical Insights from Clinopyroxene Phenocrysts into the Magma Evolution of an Alkaline Magmatic System from the Sanshui Basin, South China

The Sanshui Basin is located at the northern continental margin of the South China Sea and characterized by a continental rift basin. The bimodal volcanic rocks in Sanshui Basin record the early Cenozoic magmatic activity in the South China Block, but the magmatic evolution that produced the bimodal volcanic rocks is poorly understood. Clinopyroxenes in bimodal volcanic rocks in the Sanshui Basin provide an opportunity to investigate magma during magma ascent. In this work, we classified nine types of clinopyroxene phenocrysts according to composition and texture in cogenetic basalt-trachyandesite-comenditic trachyte, while the composition of unzoned clinopyroxene have an evolution sequence of diopside-hedenbergite-aegirine along with an increase in trace element contents with a decrease of Mg#, indicating that the genesis of clinopyroxene was dominated by fractional crystallization in a closed magma system. However, the clinopyroxenes with reversed zoning and multiple zoning record the process of magma mixing and recharge indicating an open magma system. While fractional crystallization is the dominant process, magma mixing, recharge, and crystal settling were also found to influence magma evolution. Thermobarometric calculations showed that clinopyroxene crystallized a several structural levels in the crust during magma ascent. In this study, we established a magma plumbing system that provides new constraints for the magma evolution in the Sanshui Basin.

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>

Crystal Specific Constraints on Subvolcanic Processes Preceding Eruptions at Mt Taranaki, New Zealand

<p>Andesitic magmas are the product of a complex interplay of processes including fractional crystallisation, crystal accumulation, magma mixing and crustal assimilation. Recent studies have suggested that andesitic rocks are in many cases a complex mixture of a crystal cargo and melts with more silicic compositions than andesite. In situ glass- and mineral-specific geochemical techniques are therefore key to unravelling the processes and timescales over which andesitic magmas are produced, assembled and transported to the surface. To this end, this thesis presents a detailed in situ glass- and mineral-specific study of six Holocene eruptions (Kaupokonui, Maketawa, Inglewood a and b, and Korito) at Mt Taranaki to investigate the petrogenetic processes responsible for producing these sub-plinian eruptions at this long-lived (130 000 yr) andesitic volcano. Mt Taranaki is an andesitic stratovolcano located on the west coast of New Zealand’s North Island and as such it is distinct from the main subduction related volcanism. Crystal-specific major and trace element data were combined with textural analysis and quantitative modelling of intensive magmatic parameters and crystal residence times to identify distinct mineral populations and constrain the magmatic histories of the crystal populations. Least-squares mixing modelling of glass and phenocryst compositions demonstrates that the andesitic compositions of bulk rock Mt Taranaki eruptives results from mixing of a daciticrhyolitic melt and a complex crystal cargo (plagioclase, pyroxene, amphibole) that crystallised from multiple melts under a wide range of crustal conditions. Magma mixing of compositionally similar end members that mix efficiently also occurred beneath Mt Taranaki, and as such only produced prominent disequilibrium textures in a small proportion of the minerals in the crystal cargo. The chemistry of the earliest crystallising amphibole indicates crystallisation from an andesitic-dacitic melt at depths of ca. 20-25 km, within the lower crust. Magmas then ascended through the crust relatively slowly via a complex magmatic plumbing system. However, most of the crystal cargo formed by decompression-driven crystallisation at depth so 6-10 km, as is indicated by the dominance of oscillatory zoning and the equilibrium obtained between mineral rims and the host glasses. Taranaki magmas recharge on timescales of 1000-2000 yrs. The eruptions investigated here provide a snapshot of the end of one cycle and the beginning of another. The younger Kaupokonui and Maketawa eruptions (ca. 2890 - <1950 yr BP) are the least evolved magmas, record a stronger mixing signal in the crystal cargo, and are volumetrically smaller than the earlier Inglewood a and b and Korito eruptions (ca. 4150-3580 yr BP). The Kaupokonui and Maketawa eruptions may reflect arrival of a new pulse of magma from the lower crust, or that these are early eruptions within a recharge sequence, which have not had as much time to further differentiate and evolve as the earlier Inglewood a and b and Korito eruptions that represent the end of a magma recharge cycle. One of the six investigated eruptions was identified to come from Fantham’s Peak on the basis of its distinctive glass and mineral chemistry and petrology. Glass trace element data indicate that this eurption’s magmatic system was distinct from that of the other main vent Holocene eruptions investigated in this study. Crystal residence times were investigated using Fe-Mg interdiffusion in clinopyroxene and indicate that magma bodies stall in upper crustal storage chambers for timescales of a few months to years. The younger eruptions of the least evolved magmas with the strongest mixing signal return the shortest residence times, which may indicate that magma mixing events occurring a few months before eruption may have been the trigger for these eruptions at Mt Taranaki. Amphibole geospeedometry for these eruptives reveal rapid magma transport from depths of 6-10 km to the surface on timescales of < 1 week.</p>

Crystal Specific Constraints on Subvolcanic Processes Preceding Eruptions at Mt Taranaki, New Zealand

<p>Andesitic magmas are the product of a complex interplay of processes including fractional crystallisation, crystal accumulation, magma mixing and crustal assimilation. Recent studies have suggested that andesitic rocks are in many cases a complex mixture of a crystal cargo and melts with more silicic compositions than andesite. In situ glass- and mineral-specific geochemical techniques are therefore key to unravelling the processes and timescales over which andesitic magmas are produced, assembled and transported to the surface. To this end, this thesis presents a detailed in situ glass- and mineral-specific study of six Holocene eruptions (Kaupokonui, Maketawa, Inglewood a and b, and Korito) at Mt Taranaki to investigate the petrogenetic processes responsible for producing these sub-plinian eruptions at this long-lived (130 000 yr) andesitic volcano. Mt Taranaki is an andesitic stratovolcano located on the west coast of New Zealand’s North Island and as such it is distinct from the main subduction related volcanism. Crystal-specific major and trace element data were combined with textural analysis and quantitative modelling of intensive magmatic parameters and crystal residence times to identify distinct mineral populations and constrain the magmatic histories of the crystal populations. Least-squares mixing modelling of glass and phenocryst compositions demonstrates that the andesitic compositions of bulk rock Mt Taranaki eruptives results from mixing of a daciticrhyolitic melt and a complex crystal cargo (plagioclase, pyroxene, amphibole) that crystallised from multiple melts under a wide range of crustal conditions. Magma mixing of compositionally similar end members that mix efficiently also occurred beneath Mt Taranaki, and as such only produced prominent disequilibrium textures in a small proportion of the minerals in the crystal cargo. The chemistry of the earliest crystallising amphibole indicates crystallisation from an andesitic-dacitic melt at depths of ca. 20-25 km, within the lower crust. Magmas then ascended through the crust relatively slowly via a complex magmatic plumbing system. However, most of the crystal cargo formed by decompression-driven crystallisation at depth so 6-10 km, as is indicated by the dominance of oscillatory zoning and the equilibrium obtained between mineral rims and the host glasses. Taranaki magmas recharge on timescales of 1000-2000 yrs. The eruptions investigated here provide a snapshot of the end of one cycle and the beginning of another. The younger Kaupokonui and Maketawa eruptions (ca. 2890 - <1950 yr BP) are the least evolved magmas, record a stronger mixing signal in the crystal cargo, and are volumetrically smaller than the earlier Inglewood a and b and Korito eruptions (ca. 4150-3580 yr BP). The Kaupokonui and Maketawa eruptions may reflect arrival of a new pulse of magma from the lower crust, or that these are early eruptions within a recharge sequence, which have not had as much time to further differentiate and evolve as the earlier Inglewood a and b and Korito eruptions that represent the end of a magma recharge cycle. One of the six investigated eruptions was identified to come from Fantham’s Peak on the basis of its distinctive glass and mineral chemistry and petrology. Glass trace element data indicate that this eurption’s magmatic system was distinct from that of the other main vent Holocene eruptions investigated in this study. Crystal residence times were investigated using Fe-Mg interdiffusion in clinopyroxene and indicate that magma bodies stall in upper crustal storage chambers for timescales of a few months to years. The younger eruptions of the least evolved magmas with the strongest mixing signal return the shortest residence times, which may indicate that magma mixing events occurring a few months before eruption may have been the trigger for these eruptions at Mt Taranaki. Amphibole geospeedometry for these eruptives reveal rapid magma transport from depths of 6-10 km to the surface on timescales of < 1 week.</p>

Assembling Dacite in a Continental Subduction Zone: A Case Study of Tauhara Volcano

<p>Mount Tauhara is the largest dacitic volcanic complex of onshore New Zealand and comprises seven subaerial domes and associated lava and pyroclastic flows, with a total exposed volume of ca. 1 km3. The dacites have a complex petrography including quartz, plagioclase, amphibole, orthopyroxene, clinopyroxene, olivine and Fe‐Ti oxides and offer an excellent opportunity to investigate the processes and timescales involved in assembling dacitic magma bodies in a continental subduction zone with in situ and mineral specific analytical techniques. Whole rock major and trace element data and Pb isotopes ratios define linear relationships indicating that the dacites are generated by mixing of silicic and mafic magmas. Two groups of samples define separate mixing trends between four endmembers on the basis of La/Yb ratios, 87Sr/86Sr ratios and Sr contents. The older Western and Central Domes have low 87Sr/86Sr (0.7042‐0.7046) and high LREE/HREE (LaN/YbN = 8.0‐11.5) and Sr (380‐650 ppm) compared to the younger Hipaua, Trig M, Breached and Main Domes, which have higher 87Sr/86Sr (0.7047‐0.7052) and lower LREE/HREE (LaN/YbN = 6.5‐7.5) and Sr (180‐400 ppm). In situ mineral major and trace element chemistry of mineral phases, as well as Sr and Pb isotope ratios of mineral separates have been used to: (i) fingerprint the origin of each crystal phase; (ii) constrain the chemistry of the four endmembers involved in the mixing events and; (iii) estimate the timing of mixing relative to eruption and the ascent rate of the dacitic magmas. The presence of quartz and analyses of quartz‐hosted melt inclusions are used to fingerprint the chemistry of the silicic endmembers, which is a rhyolitic melt with a major element chemistry similar to that of either the Whakamaru Group Ignimbrite melts (Western, Central and Trig M Domes) or intermediate between that of the Whakamaru and the Oruanui Ignimbrite melts (Hipaua, Breached and Main Domes). Similarly, Ba‐Sr concentrations and Sr isotopic signatures of plagioclase show that this phenocryst phase also predominantly crystallized from the rhyolitic melt. Variations in the Mg# and trace element chemistry of clinopyroxenes suggest they were formed both in the mixed dacitic melts and in a mafic endmember. The chemistry of the mafic endmembers have been traced using a combination of back‐calculated Sr melt concentrations from clinopyroxene with the highest Mg# in each sample group, and the linear trends between whole rock SiO2 content and most elements. These results indicate that dacites erupted from the Western and Central Dome were generated by the mixing of a high alumina basalt and a rhyolitic melt and Trig M Dome dacites were generated by the mixing of an andesite with a rhyolitic melt. Magmas erupted from Hipaua, Breached and Main Domes were also produced by the mixing of an andesitic melt and a rhyolitic body with a composition intermediate between that of the Whakamaru and the Oruanui melt bodies. Trace element data and 87Sr/86Sr ratios of amphibole demonstrate that it crystallized from the mixed dacitic melt. Thermobarometric conditions obtained from amphibole indicate that the magma mixing event that produced the dacites occurred within a magma chamber located at ca. 9 km depth and ca. 900°C with the exception of Trig M Dome which occurred deeper at 13 km and 950°C. Diffusion profiles of Ti in quartz and Fe‐Mg in clinopyroxene indicate the magma mixing events occurred < 6 months prior to eruption. Amphibole reaction rims show the magma to have ascended over 2‐3 weeks for each dome, with the exception of Main Dome where reaction rims were not present in the amphibole, suggesting the ascent rate was faster than 0.2 m/s (< 6 hours).</p>

Assembling Dacite in a Continental Subduction Zone: A Case Study of Tauhara Volcano

<p>Mount Tauhara is the largest dacitic volcanic complex of onshore New Zealand and comprises seven subaerial domes and associated lava and pyroclastic flows, with a total exposed volume of ca. 1 km3. The dacites have a complex petrography including quartz, plagioclase, amphibole, orthopyroxene, clinopyroxene, olivine and Fe‐Ti oxides and offer an excellent opportunity to investigate the processes and timescales involved in assembling dacitic magma bodies in a continental subduction zone with in situ and mineral specific analytical techniques. Whole rock major and trace element data and Pb isotopes ratios define linear relationships indicating that the dacites are generated by mixing of silicic and mafic magmas. Two groups of samples define separate mixing trends between four endmembers on the basis of La/Yb ratios, 87Sr/86Sr ratios and Sr contents. The older Western and Central Domes have low 87Sr/86Sr (0.7042‐0.7046) and high LREE/HREE (LaN/YbN = 8.0‐11.5) and Sr (380‐650 ppm) compared to the younger Hipaua, Trig M, Breached and Main Domes, which have higher 87Sr/86Sr (0.7047‐0.7052) and lower LREE/HREE (LaN/YbN = 6.5‐7.5) and Sr (180‐400 ppm). In situ mineral major and trace element chemistry of mineral phases, as well as Sr and Pb isotope ratios of mineral separates have been used to: (i) fingerprint the origin of each crystal phase; (ii) constrain the chemistry of the four endmembers involved in the mixing events and; (iii) estimate the timing of mixing relative to eruption and the ascent rate of the dacitic magmas. The presence of quartz and analyses of quartz‐hosted melt inclusions are used to fingerprint the chemistry of the silicic endmembers, which is a rhyolitic melt with a major element chemistry similar to that of either the Whakamaru Group Ignimbrite melts (Western, Central and Trig M Domes) or intermediate between that of the Whakamaru and the Oruanui Ignimbrite melts (Hipaua, Breached and Main Domes). Similarly, Ba‐Sr concentrations and Sr isotopic signatures of plagioclase show that this phenocryst phase also predominantly crystallized from the rhyolitic melt. Variations in the Mg# and trace element chemistry of clinopyroxenes suggest they were formed both in the mixed dacitic melts and in a mafic endmember. The chemistry of the mafic endmembers have been traced using a combination of back‐calculated Sr melt concentrations from clinopyroxene with the highest Mg# in each sample group, and the linear trends between whole rock SiO2 content and most elements. These results indicate that dacites erupted from the Western and Central Dome were generated by the mixing of a high alumina basalt and a rhyolitic melt and Trig M Dome dacites were generated by the mixing of an andesite with a rhyolitic melt. Magmas erupted from Hipaua, Breached and Main Domes were also produced by the mixing of an andesitic melt and a rhyolitic body with a composition intermediate between that of the Whakamaru and the Oruanui melt bodies. Trace element data and 87Sr/86Sr ratios of amphibole demonstrate that it crystallized from the mixed dacitic melt. Thermobarometric conditions obtained from amphibole indicate that the magma mixing event that produced the dacites occurred within a magma chamber located at ca. 9 km depth and ca. 900°C with the exception of Trig M Dome which occurred deeper at 13 km and 950°C. Diffusion profiles of Ti in quartz and Fe‐Mg in clinopyroxene indicate the magma mixing events occurred < 6 months prior to eruption. Amphibole reaction rims show the magma to have ascended over 2‐3 weeks for each dome, with the exception of Main Dome where reaction rims were not present in the amphibole, suggesting the ascent rate was faster than 0.2 m/s (< 6 hours).</p>