abstract: Hydrogen isotope compositions of the martian atmosphere and crustal materials can provide unique insights into the hydrological and geological evolution of Mars. While the present-day deuterium-to-hydrogen ratio (D/H) of the Mars atmosphere is well constrained (~6 times that of terrestrial ocean water), that of its deep silicate interior (specifically, the mantle) is less so. In fact, the hydrogen isotope composition of the primordial martian mantle is of great interest since it has implications for the origin and abundance of water on that planet. Martian meteorites could provide key constraints in this regard, since they crystallized from melts originating from the martian mantle and contain phases that potentially record the evolution of the H2O content and isotopic composition of the interior of the planet over time. Examined here are the hydrogen isotopic compositions of Nominally Anhydrous Phases (NAPs) in eight martian meteorites (five shergottites and three nakhlites) using Secondary Ion Mass Spectrometry (SIMS). This study presents a total of 113 individual analyses of H2O contents and hydrogen isotopic compositions of NAPs in the shergottites Zagami, Los Angeles, QUE 94201, SaU 005, and Tissint, and the nakhlites Nakhla, Lafayette, and Yamato 000593. The hydrogen isotopic variation between and within meteorites may be due to one or more processes including: interaction with the martian atmosphere, magmatic degassing, subsolidus alteration (including shock), and/or terrestrial contamination. Taking into consideration the effects of these processes, the hydrogen isotope composition of the martian mantle may be similar to that of the Earth. Additionally, this study calculated upper limits on the H2O contents of the shergottite and nakhlite parent melts based on the measured minimum H2O abundances in their maskelynites and pyroxenes, respectively. These calculations, along with some petrogenetic assumptions based on previous studies, were subsequently used to infer the H2O contents of the mantle source reservoirs of the depleted shergottites (200-700 ppm) and the nakhlites (10-100 ppm). This suggests that mantle source of the nakhlites is systematically drier than that of the depleted shergottites, and the upper mantle of Mars may have preserved significant heterogeneity in its H2O content. Additionally, this range of H2O contents is not dissimilar to the range observed for the Earth’s upper mantle. / Dissertation/Thesis / Masters Thesis Geological Sciences 2015

One of the most important volatiles in magma is water. In magma, water is incorporated in both the melt and in crystals, including hydrous and nominally anhydrous minerals (NAMs). The purpose of this study is to determine the role of magmatic water content in controlling volcano explosivity especially at Merapi volcano, Indonesia, which is one of the most active volcanoes in the world. Here I apply clinopyroxene from two types of eruption products, lava and ash, to test the magmatic water content in the Merapi 2010 eruption. Both oriented and unoriented crystals were analysed using Fourier-Transformed Infrared (FTIR) spectroscopy to establish the clinopyroxene’s crystal water content. By combining the water content of clinopyroxene and geochemical data obtained from EPMA analysis, the magmatic water content is then estimated by inserting the data into the equation of O’Leary et al. (2010) [lnD= -4.2(60.2)16.5(60.5) VI[Al3+]-1.0(60.2) [Ca2+]]. I also investigated clinopyroxene crystals that were experimentally rehydrated, including four oriented crystals from a Merapi 2010 eruption ash sample annealed at a temperature of 700°C and pressure of 1 atm. Magmatic water contents of Merapi 2010 from rehydration experiments were then compared to the Merapi 2006 magmatic water content which were treated under the same conditions. The results revealed a wide variation between samples and among crystals taken from the same sample. However, oriented samples yielded a smaller variation between minimum and maximum clinopyroxene crystal water content and, overall, ash samples yielded higher water content in clinopyroxene than lava samples. The rehydration experiment significantly amplified clinopyroxene crystal water content by 3 to 7-fold compared to the result without the rehydration procedure. Comparison of data between the 2006 and 2010 Merapi eruptions demonstrates that there was a significant difference in magmatic water contents with the 2010 eruption displaying more than twice as much magmatic water than the 2006 eruption. The result implies that magmatic water plays potentially a crucial role in controlling explosivity of Merapi eruptions. / Indonesien är det land i Världen som har den största befolkningen som lever inom 100 km av en aktiv vulkan. Merapi är en av de mest farliga vulkanerna i Indonesien, som också är en av de mest aktiva vulkanerna i Världen och ligger på ön Java runt 15-25 km från Yogyakarta med en total befolkningstäthet på 1000 personer per kvadratkilometer. Utbrott från Merapi har dödat cirka 5000 personer under de senaste 500 åren. Således är det viktigt att studera hur vulkanen beter sig och orsaken till utbrotten för att kunna vita förebyggande åtgärder för att minska antalet dödsfall eller till och med undvika dödsfall helt. Vulkanutbrott kontrolleras av många faktorer, en av faktorerna är flyktiga ämnen i magman och en av de viktigaste flyktiga ämnen är vatten. Det här projektet syftar till att ta reda på vattnets roll på explosiviteten hos utbrotten genom att undersöka eruptiva produkter från utbrotten av Merapi under 2006 och 2010 med hjälp av Fourier-Transformed Infrared (FTIR) spektroskopi. Experimentet använder normalt vattenfria mineraler (NAMs) så som klinopyroxen men vatten kan införlivas i NAMs genom att binda väte i kristallgitteret under kristalltillväxten. Tidigare studier har visat att vattenhalten i klinopyroxenkristall skulle kunna användas för att beräkna magmatisk vattenhalt och därmed jämföra den magmatiska vattenhalt mellan olika utbrott med olika explosivitet i samma vulkan, vilket kan indikera hur vattenhalten påverkar vulkanutbrotten. Magmatiskt vatteninnehåll beräknat utifrån klinopyroxenvattenhalten visade en variation mellan de undersöka proverna från samma utbrott, varför ytterligare undersökning genom rehydreringsexperiment gjordes genom annealing av proverna vid en temperatur av 700 °C och tryck vid 1 atm. Även om det var variation i magmatisk vattenhalt mellan proverna, så har utbrotten av Merapi under 2010 högre magmatiskt vatteninnehåll än utbrottet under 2006 med 3-7 gånger. Sammantaget har Merapi 2010 utbrottet högre explosivitet och högre magmatisk vattenhalt än 2006 utbrottet, vilket innebär att högre vattenhalt ger högre explosivitet. På detta sätt kontrollerade vattnet vulkanens explosivitet för Merapivulkanen.Nyckelord: Merapi vulkan, NA

The aim of this thesis is to increase our knowledge and understanding of trace water concentrations in nominally anhydrous minerals (NAMs). Special focus is put on the de- and rehydration mechanisms of clinopyroxene crystals in volcanic systems, how these minerals can be used to investigate the volatile content of mantle rocks and melts on both Earth and other planetary bodies (e.g., Mars). Various analytical techniques for water concentration analysis were evaluated. The first part of the thesis focusses on rehydration experiments in hydrogen gas at 1 atm and under hydrothermal pressures from 0.5 to 3 kbar on volcanic clinopyroxene crystals in order to test hydrogen incorporation and loss from crystals and how their initial water content at crystallization prior to dehydration may be restored. The results show that extensive dehydration may occur during magma ascent and degassing but may be hindered by fast ascent rates with limited volatile loss. De- and rehydration processes are governed by the redox-reaction OH- + Fe2+ ↔ O2- + Fe3+ + ½ H2. Performing rehydration experiments at different pressures can restore the water contents of clinopyroxene at various levels in the volcanic systems. Subsequently water contents of magmas and mantle sources can be deduced based on crystal/melt partition coefficients. This thesis provides examples from the Canary Islands, Merapi volcano in Indonesia and the famous Nakhla meteorite. Using NAMs as a proxy for magmatic and mantle water contents may provide a very good method especially for planetary science where sample material is limited. The thesis’ second part focusses on analytical methods to measure the concentration of water in NAMs. Specifically the application of Raman spectroscopy and proton-proton scattering are tested. The hydrated mineral zoisite is thoroughly analyzed in order to be used as an external standard material. Polarized single crystal spectra helped to determine the orientation of the OH-dipole in zoisite. Further, Transmission Raman spectroscopy and a new method for the preparation of very thin samples for proton-proton scattering were developed and tested. The results provide new possibilities for the concentration analysis of water in NAMs such as three dimensional distribution and high spatial resolution.

The Cape Verde archipelago is located 2000 km east of the Atlantic oceanic ridge and 500 km west of the western part of Africa. The plateau of the archipelago rises on average 2 km above the seafloor, which makes it one of the highest oceanic plateaus on Earth. Cape Verde originates from hotspot formation, a geological phenomenon which takes place beyond the tectonic plate boundaries where magma rises to the surface. In this thesis, volcanic material taken from the Charles Darwin volcanic field at a depth of more than 3000 meter and made up by four basaltic rocks and one agglomerate will be investigated. The agglomerate and vesicles in the rock shows that explosive volcanism occurs in high water depths, which is generally not common. Therefore, the material will be investigated to find out how explosive volcanism can occur at high water depths. The investigation will be based on quantifying the number of vesicles to able to calculate their area and analyze the magmatic water content in clinopyroxene crystals taken from the agglomerate by FTIR spectroscopy. Water is a volatile substance in the composition of magma and has a huge effect on its behavior at eruption. The results of quantification show that the area taken by vesicles varies from 7- 54 % which shows that magmatic products with high number of vesicles are common. The FTIR analysis shows that the magmatic water content can be high enough to cause an oversaturated magma system, which creates explosive eruptions. This statement is based on only one clinopyroxene crystal that had a magmatic water content of 3,87 ± 0,77 %. Other possible reasons for explosive eruptions at high water depth are the CO2 content in the magma and the size of volcanic vent. / Kap Verde är en arkipelag, situerad cirka 2000 km öster om den mittatlantiska spridningsryggen och 500 km väster om det afrikanska fastlandet. Arkipelagens platå har en genomsnittlig höjd på 2 km, vilket gör den till en av världens högsta oceaniska platåer. Arkipelagen har uppkommit av hetfläcksbildning, ett geologiskt fenomen baserad på att magma erupteras till ytan där jordskorpan är förtunnad och inte har någon anknytning till de tektoniska plattgränserna. Det som undersöks i detta kandidatarbete är vulkaniskt material, taget från den vulkaniska undervattensön Charles Darwin vulkanfält som ligger i den västra del Kap Verdes norra ö-grupp på över 3000 meterdjup. Materialet består av ett agglomerat och fyra stenstuffer av basaltisk komposition. Agglomeratet tyder på att explosiva vulkanutbrott förekommer, vilket även bekräftas av stenstufferna som har rikligt förekomst av luftbubblor. Explosiva vulkanutbrott är generellt inte förekomliga vid höga vattendjup, därav undersöks materialet för att kunna reda ut orsakerna som ger upphov till förekomsten av explosiva vulkanutbrott. Undersökningen baseras på att kvantifiera luftbubblor hos stenstufferna för att kunna räkna ut arean som upptas och analysera vattenhalten i klinopyroxenkristaller i agglomeratet med hjälp av FTIR spektroskopi. Vatten tillhör de flyktiga beståndsdelar i magmas sammansättning som kallas för volatiler och utgör en viktig parameter för magmans uppträdande vid eruption. Resultatet kvantifiering av luftbubblor visar att arean som upptas av luftbubblor varierar mellan 7–54 % av stenstufferna total area, vilket understryker att magmatiska produkter med hög andel luftbubblor är förkomliga. FTIR analysen visar att det finns tillräckliga höga vattenhalter för ett övermättat magmasystem som ger upphov till vulkanutbrott med explosiva förlopp, baserat på vattenhalten 3,87 ± 0,77 % av en klinopyroxenkristall. Andra möjliga orsaker till uppkomsten av magmatiska produkter med hög andel luftbubblor är koldioxidhalten i magman och storleken på vulkanrören.