Volcanic and magmatic processes are controlled by the composition of the magmas involved and the nature and structure of their underlying plumbing systems. To understand and predict volcanic behaviour, it is of critical importance to characterize the associated magmatic plumbing and supply system. This study investigates the magma plumbing system beneath Bali, Indonesia by employing several thermobarometric models using mineral phases in lavas from the simultaneous eruptions of Agung and Batur volcanoes in 1963 and the 1974 eruption of Batur. Compositional data were acquired from feldspar, pyroxene, and olivine crystals, using electron microprobe analysis, as well as from whole-rock samples using inductively coupled plasma mass spectrometry. Clinopyroxene-melt and clinopyroxene composition thermobarometers were then applied to equilibrated clinopyroxene-melt couples, while plagioclase-melt thermobarometry was employed on equilibrated plagioclase-melt pairs. The results were used to construct comprehensive magmatic plumbing models for Agung and Batur and are compared with geochemical, geophysical and petrological data on these volcanoes and others in the region. For the 1963 Agung eruption, results from clinopyroxene-melt thermobarometry suggest dominant crystallisation levels between 18 and 22 km depth. Clinopyroxene from the 1963 eruption of Batur record crystallisation depths between 12 and 18 km, whereas clinopyroxene from the 1974 Batur eruption show a main crystallisation level between 15 and 19 km. Furthermore, plagioclase-melt thermobarometry indicates the existence of shallow level magma reservoirs, with depths between 3 and 7 km for the 1963 eruption of Agung, between 2 and 4 km for the 1963 Batur eruption and between 3 and 5 km for the 1974 Batur event. The deep magma storage regions notably coincide with lithological boundaries in the crust and mantle beneath Bali, while the shallow reservoirs are consistent with recent geophysical studies that point to regional shallow-level magma storage. An along-arc comparison reveals this trend to be characteristic of Sunda arc magma storage systems and highlights the utility of a thermobarometric approach to detect multi-level systems beneath recently active volcanic systems.

Clinopyroxene, olivine, plagioclase and hydrous fluid lithium partition coefficients have been measured between 800-1100oC at 1 GPa. Clinopyroxene-fluid partitioning is a function of temperature (ln DLicpx/fluid = -7.3 (+0.5) + 7.0 (+0.7) * 1000/T) and appears to increase with increasing pyroxene Al2O3 content. Olivine-fluid partitioning of lithium is a function of temperature (ln DLiol/fluid = -6.0 (+2.0) + 6.5 (+2.0) * 1000/T) and appears to be sensitive to olivine Mg/Fe content. Anorthite-fluid lithium partitioning is a function of feldspar composition, similar to the partitioning of other cations in the feldspar-fluid system. Isotopic fractionation between clinopyroxene and fluid, Licpx-fluid, has been measured between 900-1100oC and ranges from -0.3 to -3.4 ‰ (±1.4 ‰). Lithium diffusion has been measured in clinopyroxene at 800-1000oC and in olivine at 1000oC. The lithium diffusion coefficient is independent of the diffusion gradient as values are the same if the flux of lithium is into or out of the crystal and ranges from -15.19 ± 2.86 m2/s at 800oC to -11.97 ± 0.86 m2/s at 1000oC. Lithium diffusion in olivine was found to be two orders of magnitude slower than for clinopyroxene at similar conditions. Closure temperatures calculated for lithium diffusion in clinopyroxene range from ~400 to ~600oC. These results demonstrate that lithium equilibration between fluids and minerals is instantaneous, on a geological timescales. The confirmation of instantaneous equilibration, combined with min-fluid partition coefficients and values for Licpx-fluid, permits quantitative modeling of the evolution of lithium concentration and isotopic composition in slab-derived fluids during transport to the arc melt source. Our results indicate that fluids migrating by porous flow will rapidly exchange lithium with the mantle, effectively buffering the fluid composition close to ambient mantle values, and rapidly attenuating the slab lithium signature. Fluid transport mechanisms involving fracture flow are required to maintain a slab-like lithium signature (both elemental and isotopic) from the slab to the melt source of island arc basalts. This study demonstrates that mineral-fluid equilibration is rapid, and as a result the lithium content of minerals can only reliably represent chemical exchange in the very latest stages of the sample’s history.

Clinopyroxene, olivine, plagioclase and hydrous fluid lithium partition coefficients have been measured between 800-1100oC at 1 GPa. Clinopyroxene-fluid partitioning is a function of temperature (ln DLicpx/fluid = -7.3 (+0.5) + 7.0 (+0.7) * 1000/T) and appears to increase with increasing pyroxene Al2O3 content. Olivine-fluid partitioning of lithium is a function of temperature (ln DLiol/fluid = -6.0 (+2.0) + 6.5 (+2.0) * 1000/T) and appears to be sensitive to olivine Mg/Fe content. Anorthite-fluid lithium partitioning is a function of feldspar composition, similar to the partitioning of other cations in the feldspar-fluid system. Isotopic fractionation between clinopyroxene and fluid, Licpx-fluid, has been measured between 900-1100oC and ranges from -0.3 to -3.4 ‰ (±1.4 ‰). Lithium diffusion has been measured in clinopyroxene at 800-1000oC and in olivine at 1000oC. The lithium diffusion coefficient is independent of the diffusion gradient as values are the same if the flux of lithium is into or out of the crystal and ranges from -15.19 ± 2.86 m2/s at 800oC to -11.97 ± 0.86 m2/s at 1000oC. Lithium diffusion in olivine was found to be two orders of magnitude slower than for clinopyroxene at similar conditions. Closure temperatures calculated for lithium diffusion in clinopyroxene range from ~400 to ~600oC. These results demonstrate that lithium equilibration between fluids and minerals is instantaneous, on a geological timescales. The confirmation of instantaneous equilibration, combined with min-fluid partition coefficients and values for Licpx-fluid, permits quantitative modeling of the evolution of lithium concentration and isotopic composition in slab-derived fluids during transport to the arc melt source. Our results indicate that fluids migrating by porous flow will rapidly exchange lithium with the mantle, effectively buffering the fluid composition close to ambient mantle values, and rapidly attenuating the slab lithium signature. Fluid transport mechanisms involving fracture flow are required to maintain a slab-like lithium signature (both elemental and isotopic) from the slab to the melt source of island arc basalts. This study demonstrates that mineral-fluid equilibration is rapid, and as a result the lithium content of minerals can only reliably represent chemical exchange in the very latest stages of the sample’s history.

Variations in major, minor, and trace elements compositions and ratios, as well as isotope ratios are all useful tools in studying the composition of the Earth’s mantle, and heterogeneities present therein. Since the mantle itself doesn’t easily lend itself to study, ocean island basalt (OIBs) are commonly used as a proxy due to compositional differences combined with the range of origination depth, a combination that allows them to represent the heterogeneity of the mantle, sampling everything from the core mantle boundary to the old or recent additions of recycled oceanic crust. Fogo, being one of the most active volcanoes in the world, continuously samples the interior of our planet, and as such is a prime location for studies of mantle geochemistry. This study aims to determine the origin of the mantle lithologies present at Fogo. The study is a continuation and extension of the studies conducted by Barker et al. (2014) and Magnusson (2016). This study utilises major, minor, and trace element geochemistry in clinopyroxene and olivine phenocrysts, as well as Ni-isotopes from whole rock samples. Using the relative values of Ni, Mn, and trace elements and their ratios in olivine and clinopyroxene phenocrysts we aim to further unravel the mechanics of the creation of ocean islands and provide additional constraints regarding the mechanics of the formation of heterogeneities in the Earth’s mantle. This study will focus on Ni* and Mn* in olivine phenocrysts, trace element composition and ratios of olivine phenocrysts and clinopyroxene phenocrysts, and Ni-isotope data.  This study found evidence for both pyroxenite, carbonatite, and carbonated eclogite source lithologies at Fogo. A correlation between La/Sm and δ60Ni was also found, indicating a control on the δ60Ni by source pyroxenite. This study suggests a carbonated eclogite origin for the lithologies present at Fogo, which would have hosted the majority of the olivine phenocrysts. The phenocrysts then resided within a separated carbonatite melt fraction that either contaminated or metasomatized a pyroxenite melt where the clinopyroxene phenocrysts nucleated. The melt then evolved to an alkali basalt melt through melt-rock reactions, principally via the dissolution of orthopyroxenes and concomitant precipitation of clinopyroxene and olivine (Zhang, Chen, Jackson & Hofmann 2017).

abstract: Volcanic eruptions are serious geological hazards; the aftermath of the explosive eruptions produced at high-silica volcanic systems often results in long-term threats to climate, travel, farming, and human life. To construct models for eruption forecasting, the timescales of events leading up to eruption must be accurately quantified. In the field of igneous petrology, the timing of these events (e.g. periods of magma formation, duration of recharge events) and their influence on eruptive timescales are still poorly constrained. In this dissertation, I discuss how the new tools and methods I have developed are helping to improve our understanding of these magmatic events. I have developed a method to calculate more accurate timescales for these events from the diffusive relaxation of chemical zoning in individual mineral crystals (i.e., diffusion chronometry), and I use this technique to compare the times recorded by different minerals from the same Yellowstone lava flow, the Scaup Lake rhyolite. I have also derived a new geothermometer to calculate magma temperature from the compositions of the mineral clinopyroxene and the surrounding liquid. This empirically-derived geothermometer is calibrated for the high FeOtot (Mg# = 56) and low Al2O3 (0.53–0.73 wt%) clinopyroxene found in the Scaup Lake rhyolite and other high-silica igneous systems. A determination of accurate mineral temperatures is crucial to calculate magmatic heat budgets and to use methods such as diffusion chronometry. Together, these tools allow me to paint a more accurate picture of the conditions and tempo of events inside a magma body in the millennia to months leading up to eruption. Additionally, I conducted petrological experiments to determine the composition of hypothetical exoplanet partial mantle melts, which could become these planets’ new crust, and therefore new surface. Understanding the composition of an exoplanet’s crust is the first step to understanding chemical weathering, surface-atmosphere chemical interactions, the volcanic contribution to any atmosphere present, and biological processes, as life depends on these surfaces for nutrients. The data I have produced can be used to predict differences in crust compositions of exoplanets with similar bulk compositions to those explored herein, as well as to calibrate future exoplanet petrologic models. / Dissertation/Thesis / Doctoral Dissertation Geological Sciences 2020

A young marine island called Heard Island is located in the southern Kerguelen Plateau in the Indian Ocean, a large igneous province created by the Kerguelen mantle plume. The two major geographic regions on Heard Island have two principal volcano-magmatic suites. Basanites, alkali basalts, and trachybasalts make up one group, the Big Ben Series (BBS), while basanitic to trachytic rocks make up the Laurens Peninsula Series (LPS). The most recent eruption at Big Ben volcano occurred in October 2022. To better understand magma evolution in the underlying plumbing system, clinopyroxene, feldspar, and olivine, mineral chemistry, clinopyroxene thermobarometry, and olivine thermometry were used.      The main phenocrysts from Heard Island are olivine, clinopyroxene, and feldspar. All phenocrysts share the characteristics of sieve textures and fractures. The mineral chemistry of clinopyroxene, zonation, and variation of core and rim of Mg#, Al2O3, TiO2, and Cr2O3, provides insight into the magmatic evolution of magma. Results from clinopyroxene-liquid thermobarometry suggest that clinopyroxene crystallization occurs at depths of 1 to 39 km for the cores and 1 to 47 km for the rims, with corresponding temperatures of 1098 to 1208°C and 1099 to 1254°C respectively. Comparison with olivine thermometry shows concordance in temperature estimates. The Mohorovičić discontinuity, or Moho, which marks the boundary between the Earth's crust and mantle, is believed to lie between 18 and 26 km deep at Heard Island. This study suggests that magma pockets can be found below the Moho between 51 and 18 km, and in the upper and lower crust between 18 and 2 km. Additionally, the density difference between various crustal layers determines where magma storage is located. The evidence from petrology and geochemistry points to common processes of magma mixing, recharge, and fractional crystallization during magma evolution.

Cumulate xenoliths erupted with alkalic hawaiite lavas from a postshield cinder cone on Mauna Kea, Hawaii include a variety of mafic and ultramafic rock types. Previous studies of major and trace element compositions of minerals in the xenoliths are interpreted to show transitional to alkalic magma parentages from the postshield stage, although any orthopyroxene-bearing xenoliths are considered to have tholeiitic parents. Major element compositions minerals were analyzed using the electron microprobe and trace element compositions of clinopyroxene grains were analyzed by laser ablation inductively coupled plasma mass spectrometry. In this study, major element compositions of clinopyroxene, olivine and plagioclase grains and trace element compositions in clinopyroxene grains in xenoliths lacking orthopyroxene indicate a transitional magma parentage consistant with postshield magmas. Trace element compositions of possible parent magmas of the xenoliths were calculated from clinopyroxene compositions using partition coefficients for basaltic liquids from Hauri et al. (1994). Liquids calculated from the clinopyroxene in the xenoliths were compared to Mauna Kea shield lavas and to the postshield Hamakua and Laupahoehoe units. Chondrite-normalized rare earth element (REE) patterns of liquids calculated from both orthopyroxene-bearing xenoliths and those without orthopyroxene were similar REE patterns of both Mauna Kea postshield tholeitic and alkalic lavas. Liquids from a wehrlite and an olivine gabbronorite have REE patterns similar to tholeiitic shield basalts. To better distinguish the transitional xenolith sources as one of Mauna Kea's two postshield substages, the older, basaltic Hamakua unit or the younger hawaiitic Laupahoehoe unit, variation diagrams compared calculated liquid compositions to Mauna Kea lavas from the shield and postshield stages. Calculated liquid trace element concentrations are similar to those of Hamakua lavas.

No description available.

The volcanic island of Fogo belongs to the Cape Verde archipelago, a two-tiered chain of islands situated 500 km west of the African coast. Fogo is regarded as one of the most active volcanoes in the world with 10 eruptions during the last 250 years. The former shield volcano Monte Amarelo reached 3500 m.a.s.l. before it collapsed into the Atlantic Ocean. The massive landslide event occurred between 124 and 86 ka, forming the Bordeira cliffs and the high plateau Cha das Caldeiras on Fogo. We have collected rock samples from the Bordeira dikes, which intruded into the Bordeira wall prior to collapse. The purpose of the project is to produce a magmatic storage model for Fogo using mineral chemistry and thermobarometric methods. Additionally, I aim to determine the processes prevailing in the magmatic system, the link between the volcanic and plutonic system. Previous studies on the magma storage beneath Fogo have focused on the volcanics, which show crystallization pressures between 0.45 to 0.68 GPa using clinopyroxene-melt thermobarometry on rims. The Bordeira dikes are basanitic to nephelinitic in composition. The mineral assemblage of the 20 dike samples consist of phenocrystic clinopyroxene ± olivine ± plagioclase ± xenocrystic amphibole. Accessory minerals are titanomagnetite, apatite, nepheline, plagioclase and alkali feldspar in a microcrystalline groundmass. Clinopyroxene displays a large compositional variation, ranging from Mg#38 to Mg#85, with a mean of Mg#71±10 2s.d. (n=614). Xenocrystic amphibole varies from Mg#37 to Mg#72, with a mean of Mg#62±15 2s.d. (n=78). Interstitial feldspar forms two groups, one of An#24 to An#79, with a mean of An#66±19 2s.d., (n=125) and a second with Or#19 to 100 with a mean of Or#69±42 2s.d.(n=71). Bulk geochemistry of the 20 samples range from 1.82 to 11.5 MgO wt%. Our clinopyroxene-melt thermobarometry show crystallization pressures ranging from 0.02 to 0.85 GPa, with a mean of 0.47±0.29 2s.d. (n=502) (Putirka et al. 2003). Structural data from the intrusive dikes in the Bordeira contain three preferred orientations, N-S, NW-SE and E-W (n=371). The main process occurring in the magmatic system is fractional crystallization, however there is some evidence for phenocryst accumulation and magma recharge. Our magma storage model show that clinopyroxene crystallization initiates in the lithospheric mantle, between 15 to 28 km depth. Significant clinopyroxene rim and microcryst crystallization occur above Moho, between 9 to 12 km, implying that magma storage levels do exist in the oceanic crust. The intrusive and extrusive rocks present on Fogo show common storage levels, suggesting that they are formed in the same system but the difference being their residence time in the crustal level storage. Our structural data and 3D model suggest that the Monte Amarelo rift zone was composed of three components, being oriented NW-SE, N-NE and E-W. The flank collapse was caused by dike intrusions of N-S orientation which enabled a E-W extension of the shield volcano. / Vulkanön Fogo är en del av ögruppen Kap Verde i Atlanten. Ögruppen bildar en två delad arkipelag positionerad 500 km väster om det afrikanska fastlandet. Ön, tillika vulkanen Fogo har på senare tid varit en av de mest aktiva vulkanerna i världen med 10 utbrott under de senaste 250 åren. Ön byggdes upp av sköldvulkanen Monte Amarelo nådde 3500 m ö h innan delar av den kollapsade ned i Atlanten. Det massiva skredet som skedde mellan 86 och 124 tusen år sedan skapade högplatån Cha das Caldeiras samt den omringande klippsektionen Bordeira. Vi har samlat stenprover från de plutoniska bergarter som har trängt in sig i klippsektionen Bordeira. Målet med vår studie är att skapa en modell för hur magma lagringen fungerar under Fogo. Vi ämnar kartlägga magmalagringsdjupet med hjälp av kemiska variation i mineral som kan användas för att kartlägga kristalliseringstryck och temperatur som i t.ex. klinopyroxen. Vi är samtidigt intresserade av att veta vilka processer som sker i det magmatiska systemet och sambandet mellan vulkanska bergarter t.ex. lava och plutoniska bergarter. Tidigare studier av Fogos magmalagring har använt vulkaniska bergarter, som kristalliserar sig mellan 0.45 till 0.68 GPa när man undersökt kemin på kristallkanter av klinopyroxen. 20 prover har analyserats från Bordeiraklipporna och de innehåller låga kiselhalter, mellan 37 till 47% samt höga mängder alkaliska oxider så som kalium och natrium. Provernas mineralinnehåll består främst av större kristaller av silikatmineralen klinopyroxen ± olivin± fältspat ± främmande amfibolkristaller. De större kristallerna är omringande av en mikrokristallin grundmassa bestående av järn-titanoxider, apatit och fältspatoider. Klinopyroxen har en relativt stor kemisk variation, med Mg#37 till Mg#85, med ett medelvärde på Mg#71. Vi har även två olika sorter av fältspat, en grupp med ett kalciumrik rikt innehåll klassificeras som anortit, och en annan med ett kaliumrikt innehåll, som ortoklas. Vår analys av klinopyroxen-smälta har gett oss kristalliseringstryck som sträcker sig mellan 0.02 till 0.85 GPa med ett medelvärde på 0.47 GPa. Detta innebär att den dominerande processen i magmalagringssystemet är fraktionerad kristallisering då vi kan se ett linjärt avtagande för många ämnen när de jämförs mot magnesiumhalten. Vår magmalagringsmodell för vulkanen Fogo visar att klinopyroxenkrystallisering påbörjas i den litosfäriska manteln, mellan 15 och 28 km djup. Kristallisering av kanter på klinopyroxenkristaller samt mindre kristaller i grundmassan sker ytligare och visar på att det finns en eller flera magmalagringsnivåer i den oceaniska jordskorpan, mellan 9 till 12 km djup. Vulkaniska och plutoniska bergarter vittnar om ett delat magmasystem, vilket indikerar att skillnaden mellan de två bergarterna främst är tiden de befinner sig på respektive lagringsnivå. Vår strukturgeologiska data samt 3D modell visar att den intrusiva aktiviteten var primärt orienterad NV-SO, N-NO och O-Vriktning. Monte Amarelo-vulkanens skred och kollaps orsakades av intruderande gångar med en generell N-S orientering vilket ledde till ett skred på östsidan.

O grande magmatismo intracontinental ocorrido a 133 Ma na Bacia do Paraná foi desenvolvido por um sistema fissural no qual a interação da Pluma Tristão da Cunha na base da litosfera (com ou sem contaminação crustal) gerou derrames, diques e sills no Brasil, nos Estados do RS, SC, PR, SP, MT, MS e GO, e em parte do Paraguai, Argentina e Uruguai. Na Formação Serra Geral, representativa deste intenso magmatismo, foram coletadas amostras de sills (RS, PR, SP e GO) cristalizados entre os sedimentos Paleozóicos pré-vulcânicos da Bacia do Paraná. Já haviam sido realizados diversos estudos geoquímicos a partir da década de 80 com objetivo de identificar as variações químicas de diques, derrames e sills da Formação Serra Geral. No entanto, a utilização de novas técnicas analíticas (EPMA e LA-ICP-MS), utilizadas no presente estudo, proporcionaram o entendimento das variações químicas de forma pontual em minerais ígneos. A geoquímica dos sills estudados caracteriza-os como sub-alcalinos toleíticos continentais que variam de basaltos a andesitos basáltico. Assim, podendo ser divididos em dois grupos químicos: sills do Rio Grande do Sul (baixo TiO2 < 2 wt.%, com concentrações inferiores de P2O5, Nb, Sr, Zr, Zn, Y e Pb e concentrações superiores de Rb, Th, U, e Cs) e sills do Paraná, São Paulo e Goiás (alto TiO2 >2 wt.%, de geoquímica oposta). Petrograficamente, os sills do RS possuem granulação mais fina, ocorrência restrita de cobre nativo e distribuição modal elevada para plagioclásios cálcicos, quando comparados ao sills do PR, SP e GO. A determinação geoquímica por micro-análise em plagioclásios e clinopiroxênios demonstra que as variações químicas identificadas em rocha total são relatas as modificações químicas ocorridas nestes minerais. Variações do coeficiente de partição (KD) de elementos traços compatíveis em diversas zonas de cristais de plagioclásio e clinopiroxênio possuem correlação na substituição dos elementos Ca, Na, Al, Fe e Mg nos sistemas NaAlSi3O8-CaAl2Si2O8 e Mg2Si2O6-CaMgSi2O6-CaFeSi2O6- Fe2Si2O6, respectivamente. Coeficientes de partição de cristais de plagioclásio e clinopiroxênio agora são determinados em diferentes porções de núcleo, intermédio e borda aprimorando o conhecimento da variação do KD até então determinado como um único valor apenas para o cristal. / The large intracontinental magmatism occurred at 133 Ma in the Paraná Basin was developed by a fissure system in which the interaction of Tristan da Cunha plume at the base of the lithosphere (with or without crustal contamination) caused lava flows, dikes and sills in the RS, SC, PR, SP, MT, MS and GO and part of Paraguay, Argentina and Uruguay. In the Serra Geral Formation, representative of intense magmatism, sills crystallized samples were collected (RS, PR, SP and GO) between the Paleozoic prevolcanic sediments of Paraná basin. Several geochemical studies have been carried out since the 80's in order to identify the chemical variations of dikes, sills and lava flows of the Serra Geral Formation. However, the use of new analytical techniques (EPMA and LA-ICP-MS) provided the study of chemical variations in a timely manner in igneous minerals. The geochemistry of the sills studied characterized them as sub-alkaline continental tholeiitic basalts ranging from the basalt to basaltic andesites. Divided into two chemical groups: sills of Rio Grande do Sul (low TiO2 <2 wt.%, With lower concentrations of P2O5, Nb, Sr, Zr, Zn, Y and Pb and higher concentrations of Rb, Th, U, and Cs) and sills of Parana, Sao Paulo and Goiás (high TiO2> 2 wt.%, geochemical opposite). Petrographically the sills of the RS have finer grain, restricted occurrence of native copper and modal higher to calcic plagioclase, compared to the sills of the PR, SP and GO. Geochemical determination by micro-analysis in plagioclases and clinopyroxenes show that the chemical variations identified in whole rock we describe the chemical changes occurring in these minerals. Variations of the partition coefficient (KD) of compatible trace elements in various parts of crystals of plagioclase and clinopyroxene were correlated in the replacement of Ca, Na, Al, Fe and Mg systems NaAlSi3O8-CaAl2Si2O8 and Mg2Si2O6-CaMgSi2O6-CaFeSi2O6-Fe2Si2O6, respectively. Partition coefficients of crystals of plagioclase and clinopyroxene are now determined in different portions of core, intermediate and rim enhance knowledge of the variation of KD previously determined as a single value only to the crystal.