Thesis (M.S.)--Michigan State University. Geological Sciences, 2008. / Title from PDF t.p. (Proquest, viewed on Aug. 10, 2009) Includes bibliographical references (p. 87-90). Also issued in print.

Thesis (Ph. D.)--University of Washington, 2002. / Vita. Includes bibliographical references (leaves 121-129).

No description available.

Thesis (MSc)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: Entrainment and assimilation of xenolithic material during kimberlite ascent is considered to be important in shaping the chemistry of the magma and fuelling magma ascent by driving CO2 exsolution. Previous, but as yet unpublished experimental work from Stellenbosch University has demonstrated that orthopyroxene has a key role in this. Orthopyroxene is a very rare xenocrystic constituent of kimberlite but makes up a considerable fraction of the entrained xenolithic material. The initial study used a natural kimberlite composition (ADF1) doped with a peridotite mineral suite (by weight); 88 % ADF1 5% olivine, 5% orthopyroxene and 2% garnet-spinel intergrowth as a starting composition. The subsequent high PT experiments (1100 to 1300°C and 2.0 to 3.5GPa) established that equilibrium orthopyroxene is stable at 1100°C above 2.5GPa, at 1200°C above 2.5GPa and at 1300°C between 2.0 and 3.5GPa. At lower pressures orthopyroxene is completely digested by the experimental melt by the reaction; Mg2Si2O6 (opx) = Mg2SiO4 (ol) + SiO2 (in liquid). In contrast, clinopyroxene is a common phase in kimberlite and often occurs as more than one generation of crystals. Xenocrystic clinopyroxene is dominated by diopside compositions. However, rare omphacite is sometimes also inherited from an eclogite source. The Omphacite, like orthopyroxene, displays textural evidence of severe disequilibrium and may also contribute to the evolution of kimberlitic melt. Thus, a second study produced experiments on the ADF1 kimberlite material at upper mantle PT conditions (1100 to 1300°C and 2.0 to 4.0GPa) as well as an omphacite doped starting material (ADF1+O). These experiments examine the behaviour of pyroxene in kimberlite magma including the influence this may have on magma buoyancy. Within this PT range omphacitic clinopyroxene breaks-down via complex multipart reactions. At 1100°C and 2.0GPa reaction textures around remnant omphacite suggest that omphacite melts incongruently in a complex reaction similar to: Omp + Melt = Ap + Cr-diop + SiO2-enriched Melt. At 1300°C omphacite melts completely and is perceived to produce peritectic Cr-diopside, calcium-rich olivine, carbonate in the melt as well as enrich the melt in SiO2. The melts produced by both the ADF1+O and ADF1 compositions at 1300°C and 4.0GPa are reduced in SiO2 content and have increased TiO2, Cr2O3, Al2O3, MnO, CaO, K2O and P2O5 compared to their respective starting compositions. However, significantly higher proportions of Ca, Na and Fe observed within the ADF1+O melt is a direct consequence of omphacite melting. The ADF1+O starting composition produced equilibrium orthopyroxene above 1100°C and 4.0GPa as well as at 1300°C above 2.0GPa. At lower pressure the orthopyroxene melts incongruently to form peritectic olivine and more silica-rich melt compositions. This digestion favours CO2 exsolution. The effect of orthopyroxene melting can be seen in the melt compositions produced by the peridotite doped starting material (ADF1+P) of the initial study. At 1300°C and 2.0GPa, ADF1+P produced a siliceous melt (37.0 wt.% SiO2) enriched in Al and alkalis compared to the starting ADF1+P composition. This behaviour is directly attributed to xenocrystic orthopyroxene melting at high temperature. In contrast, at the same PT the original kimberlite (ADF1) composition produces a melt with 28.9 wt.% SiO2 and high Ca and Mg contents. Overall, with an increase in pressure the melts become enriched in alkalis and Al2O3 as a direct result of xenocrystic pyroxene melting. In addition, increased pressure allows for a greater solubility of CO2 within the melt. This results in a lower SiO2 melt content and the increased stabilization of equilibrium silica-rich mineral phases (i.e. olivine and equilibrium orthopyroxene). Within the peridotite doped static system (unpublished) the mineral separates with an average crystal size of 115μm ±10μm were all effectively digested in less than 48hours. Similarly, the omphacite doped experiments consumed the 150μm (±10μm) xenocrysts in under 24 hours. Thus, it is suggested that xenocrystic pyroxene is unstable in these experimental kimberlitic melt compositions and is likely to be efficiently assimilated in less than 24 hours. These experimental melts most likely resemble those of natural systems under upper mantle PT conditions. Therefore, pyroxene melting increases the silica content of the melt which in turn drives CO2 exsolution and ascent. / AFRIKAANSE OPSOMMING: Meevoering en assimilasie van xenolitiese materiaal gedurenende kimberliet bestyging is beskou as belangrik in verband met die vorming van die chemie van die magma, en bevorder magma bestyging deur die aandrywing van CO2 ontmenging. Vorige, maar ongepubliseerde eksperimentele werk vanaf Stellenbosch Universiteit het gedemonstreer dat ortopirokseen ‘n sleutelrol hierin het, omrede ortopirokseen ‘n baie skaars xenokristiese bestanddeel van kimberliet is maar ‘n aansienlike fraksie van die meevoerde xenolitiese materiaal moet opmaak. Hierdie studie het ‘n natuurlike primere kimberliet komposisie (ADFI) gedoop met ‘n peridotiet mineraal reeks (per gewig); 88 % ADF1 5% olivien, 5% ortopirokseen en 2% granaat-spinel ingroeiing as begin komposisie gebruik. Die daaropvolgende hoë DT eksperimente (1100 tot 1300°C en 2.0 tot 3.5GPa) het vasgestel dat ewewigsortopirokseen stabiel is teen 1100°C bo 2.5GPa, 1200°C bo 2.5GPa en teen 1300°C vanaf 2.0 tot 3.5Gpa. Teen laer druk word ortopirokseen geheel verteer deur die eksperimentele smelting volgens die reaksie Mg2Si2O6 (opx) = Mg2SiO4 (ol) + SiO2 (in vloeistof). In kontras hiermee is clinopirokseen algemeen in kiemberliet en kom dikwels voor as meer as een generasie se kristalle. Diopsiet komposisies domineer xenokristiese klinopirokseen. Seldsame omfasiet is tog somtyds ook geërf vanaf ‘n eklogiet bron. Die omfasiet, soos ortopirokseen, vertoon teksturuele bewys van ernstige disekwilibrium en mag ook bydra tot die evolusie van kimberlitiese smelt. Dus was daar addisionele eksperimente uitgevoer op die ADF1 kimberliet material teen hoër mantel DT kondisies (1100 tot 1300°C en 2.0 tot 4.0GPa), asook ‘n begin materiaal gedoop met omfasiet (ADF1+O). Hierdie eksperimente ondersoek die gedrag van pirokseen in kiemberliet magma, asook die invloed wat dit sal hê op die dryfvermoë van die magma. Binne hierdie DT reeks breek omfasitiese klinopirokseen af via komplekse multideel reaksie prosesse. Teen 1100°C en 2.0Gpa stel reaksie teksture rondom die oorblywende omfasiet voor dat omfasiet ongelykvormig smelt deur ‘n komplekse reaksie soortgelyk aan: Omp + Smelt = Ap + Cr-diop + SiO2-verrykde Smelt. Teen 1300°C smelt omfasiet volkome en is waargeneem om peritektiese Cr-diopsiet, kalsiumryke olivien en kalsiet te produseer, sowel as dat dit die smelt verryk in SiO2. Die smeltings geprodiseer deur die ADF1+O en ADF1 massa komposisies teen 1300°C en 4.0GPa is verlaag in SiO2 inhoud en bevat verhoogde TiO2, Cr2O3, Al2O3, MnO, CaO, K2O en P2O5 in vergelyking met die onderskeie begin komposisies. Aansienlike hoër proporsies van Ca, Na en Fe is egter waargeneem in die ADF1+O smelt en is ‘n direkte gevolg van die smelting van omfasiet. Die ADF1+O begin samestelling het ewewigsortopirokseen bo 1100°C en 4.0Gpa geproduseer en massa teen 1300°C en 2.0 tot 4.0GPa. Teen laer druk smelt hierdie pirokseen inkongruent om peritektiese olivien en meer silika-ryke smelt samestellings te vorm, en ontmeng CO2. Die effek van ortopirokseen smelting kan aanskou word in die smelt samestellings wat produseer is deur die begin materiaal wat gedoop is in peridotiet (ADF1+P), in die oorspronklike studie. Teen 1300°C en 2.0GPa het ADF1+P ‘n silikahoudende smelt (37.0 wt.% SiO2) produseer wat verryk is in Al en alkalies in vergelyking met die ADF1+P massa samestelling. Hierdie gedrag is direk toegeskryf aan die xenokristiese ortopirokseen wat smelt teen hoë temperatuur. In kontras hiermee, teen dieselfde DT kondisies produseer die oorspronklike kiemberliet (ADF1) massa ‘n smelt met 28.86 gewigspersentasie SiO2 en hoë Ca en Mg inhoud. In die algeheel word die smeltings verryk in alkalies en Al2O3 teen verhoogde druk as ‘n derekte gevolg van xenokristiese pirokseen smelting. Verder laat verhoogde druk toe vir hoër oplosbaarheid van CO2 in die smelt, wat lei tot laer SiO2 inhoud en ‘n toename in stabilisering van ewewigs silika-ryke mineraal fases (dws. olivien en ewewigsortopirokseen). In die peridotiet gedoopde statiese sisteem (ongepubliseerd), was die mineraal skeiding met ‘n gemiddelde kristal grootte van 115μm ±10μm almal effektief verteer in minder as 48 ure. Soortgelyk hieraan het die omfasiet gedoopde eksperimente die 150μm (±10μm) sade onder 24 ure verteer. Dus stel dit voor dat xenokristiese pirokseen in naatuurlike sisteme onstabiel is in kiemberlietiese smelt samestellings en sal waarskynlik geassimileer wees in miner as 24 ure en ‘n meer silica-ryke kiemberlietiese smelt samestelling produseer terwyl dit CO2, ontmenging en bestyging aandryf.

For over 100 years eclogites have played a vital role in the development of partial melting models, crustal-mantle systems and geodynamic models involving subduction/recycling processes. However their origin remains controversial from one involving subducted basaltic protoliths to polybaric fractionates of basaltic melts with the added complexity of post-formational metamorphic processes. This thesis presents new chemical data on eclogite and pyroxenite samples from varied geological settings: a classic craton [Kaapvaal Craton (e.g., Roberts Victor, Kimberley and Bultfontein pipes)], circum-cratonic localities (Chino Valley – USA) and oceanic environments (Malaita, New Zealand and Hawaii). Apart from petrographic data, mineral chemistry has been constrained using the electron microprobe and laser ablation ICP-MS for major, minor and trace element data, laser ablation for oxygen isotope data and ICP-MS and TIMS for radiogenic isotopes (Sm-Nd, Lu-Hf and Sr). Garnet pyroxenites have normalised trace element patterns and O isotopes consistent with derivation from silicate melts or by reaction between melts and peridotite. On-craton eclogites and garnet clinopyroxenites have normalised trace element patterns and heterogeneous O isotopes indicative of lower temperature processes either as (a) a “basaltic” protolith altered at low temperatures and subducted to form eclogite or (b) an eclogite retrograded to garnet pyroxenite pre- or syn-entrainment. Modeling of Hf-Nd-Sr isotopes indicates that the Kaapvaal eclogites were derived from Archean protoliths whose isotopic signatures have been disturbed by extensive metasomatism. Four aspects of the thesis are noteworthy: (1) the extreme Hf-Nd-Sr heterogeneity shown by eclogites and pyroxenites relative to MORB and OIB, (2) the heavy O isotope ratios for on- and off-craton samples from Chino Valley and Lovedale, (3) the unique Archean (3.15 Ga) low Hf, Nd and Sr reservoir represented by a Roberts Victor eclogite, and (4) the Lu-Hf system is more robust than the Sm-Nd system.

Multiple studies in the Bengal basin have shown that elevated As in groundwater coincides with reduced, relatively dark sediments of Himalayan provenance. In West Bengal state (India), As concentrations > 10 μg/L tend to occur east of the River Bhagirathi-Hoogly, the main distributary of the Ganges. Associations among sediment chemistry and mineralogy for four cores from either side of the Bhagirathi-Hoogly (cores 1 and 2 to the east, 3 and 4 to the west) in Murshidabad district were investigated. Ten sediment samples were collected from each boring at various depths to a maximum of 38 to 43 m. Sediment chemistry was investigated using sequential extraction, digestion and analysis of As, Al, Ca, Fe, and Mn on an ICP-OES and GFAAS, and by total carbon analysis on a CNS analyzer. Organic carbon content was measured gravimetrically by HCl digestion. Sediment mineralogy was investigated using thin-section petrography and a microprobe EDS. Pyroxenes and phyllosilicates appear to be the primary sources of arsenic in the study area. Additionally, core 4 sediments are mineralogically similar to cores 1 and 2 despite differences in arsenic concentrations in the groundwater. We conclude that a 65-ft (20-m) silt layer overlying the aquifer sands in core 4 acts as a local aquitard and restricts arsenic mobilization locally.

The Mont Saint-Hilaire alkaline complex, Québec, is a Cretaceous rift-related intrusion comprising two gabbroic suites and the East Hill suite, an assemblage of several distinct nepheline syenites and evolved syenitic rocks. Whole-rock analysis of the East Hill suite reveals two fractionation trends, one which is described by the syenitic lithologies and one by the evolved syenites and syenoids. A lamprophyric unit stands on its own, geochemically, consistent with typical lamprophyre petrogenesis. Whole-rock geochemistry of the East Hill suite shows moderate silica content but highly alkaline rocks, enriched in Mn, Zn, Zr, Y, and Ce. Chlorine and sulfur are important and present in abundant secondary sodalite and pervasive microsulfides. Mineral geochemistry indicates decreasing oxygen fugacity with cooling, and phases such as titanite (present) and aenigmatite (absent) defined boundaries in fO2 – T space. Oxygen fugacity data combined with petrography and geothermometry defined an 2 fO – T curve for the East Hill suite magma, revealing that the oxygen fugacity ranged between approximately 10-10 bar at intrusion down to 10-25 bar subsolidus, and that, owing to non-linearity of oxygen buffers, the 2 fO – T path crossed below QFM early, went above QFM late in the crystallization history and then above HM with cooling. A similar procedure applied to sulfur fugacity generated a trend of initial increase from about 10-4 to 10-2 bar followed by decreasing sulfur fugacity with cooling down to approximately 10-8 bar. The oxygen trend implies that earlier suggestions that oxidation of iron drove the evolution of pyroxenes towards aegirine are incorrect. Textural evidence of abundant alteration and secondary mineralization suggests subsolidus action of alkaline fluids. Contrary to previous studies, most sodalite in the East Hill suite is not primary but is the product of reaction of nepheline with chloride-rich fluids after crystallization. Sodalite pseudomorphs continued to react with these fluids, whose chemistry changed with time to silica- then carbonate-rich, resulting in further reactions that led to natrolite and dawsonite deposition, accompanied by late-stage rhodochrosite. It is hypothesized that the silica- and carbonate-rich phase of these fluids caused the decomposition of a melilite groundmass in the lamprophyre to a natrolite-calcite assemblage.

Processes that take place in the Earth’s mantle are not accessible to direct observation. Natural samples of mantle material that have been transported to the surface as xenoliths provide useful information on phase relations and compositions of phases at the pressure and temperature conditions of each rock fragment. In the past, considerable effort has been devoted by petrologists to investigate upper mantle processes experimentally. Results of high temperatures, high pressure experiments have provided insight into lower crust-upper mantle phase relations as a function of temperature, pressure and composition. However, the attainment of equilibrium in these experiments, especially in complex systems, may be very difficult to test rigorously. Furthermore, experimental results may also require extrapolation to different pressures, temperatures or bulk compositions. More recently, thermodynamic modeling has proved to be a very powerful approach to this problem, allowing the deciphering the physicochemical conditions at which mantle processes occur. On the other hand, a comprehensive thermodynamic model to investigate lower crust-upper mantle phase assemblages in complex systems does not exist. ¶ In this study, a new thermodynamic model to describe phase equilibria between silicate and/or oxide crystalline phases has been derived. For every solution phase the molar Gibbs free energy is given by the sum of contributions from the energy of the end-members, ideal mixing on sites, and excess site mixing terms. It is here argued that the end-member term of the Gibbs free energy for complex solid solution phases (e.g. pyroxene, spinel) has not previously been treated in the most appropriate manner. As an example, the correct expression of this term for a pyroxene solution in a general (Na-Ca-Mg-Fe2+-Al-Cr-Fe3+-Si-Ti) system is presented and the principle underlying its formulation for any complex solution phase is elucidated.¶ Based on the thermodynamic model an algorithm to compute lower crust-upper mantle phase equilibria for subsolidus mineral assemblages as a function of composition, temperature and pressure has been developed. Included in the algorithm is a new way to represent the total Gibbs free energy for any multi-phase complex system. At any given temperature and pressure a closed multi-phase system is at its equilibrium condition when the chemical composition of the phases present in the system and the number of moles of each are such that the Gibbs free energy of the system reaches its minimum value. From a mathematical point of view, the determination of equilibrium phase assemblages can, in short, be defined as a constrained minimization problem. To solve the Gibbs free energy minimization problem a ‘Feasible Iterate Sequential Quadratic Programming’ method (FSQP) is employed. The system’s Gibbs free energy is minimized under several different linear and non-linear constraints. The algorithm, coded as a highly flexible FORTRAN computer program (named ‘Gib’), has been set up, at the moment, to perform equilibrium calculations in NaO-CaO-MgO-FeO-Al2O3-Cr2O3-Fe2O3- SiO2-TiO2 systems. However, the program is designed in a way that any other oxide component could be easily added.¶ To accurately forward model phase equilibria compositions using ‘Gib’, a precise estimation of the thermodynamic data for mineral end-members and of the solution parameters that will be adopted in the computation is needed. As a result, the value of these parameters had to be derived/refined for every solution phase in the investigated systems. A computer program (called ‘GibInv’) has been set up, and its implementation is here described in detail, that allows the simultaneous refinement of any of the end-member and mixing parameters. Derivation of internally consistent thermodynamic data is obtained by making use of the Bayesian technique. The program, after being successfully tested in a synthetic case, is initially applied to pyroxene assemblages in the system CaO-MgO-FeO-Al2O3-SiO2 (i.e. CMFAS) and in its constituent subsystems. Preliminary results are presented.¶ The new thermodynamic model is then applied to assemblages of Ca-Mg-Fe olivines and to assemblages of coexisting pyroxenes (orthopyroxene, low Ca- and high Ca clinopyroxene; two or three depending on T-P-bulk composition conditions), in CMFAS system and subsystems. Olivine and pyroxene solid solution and end-member parameters are refined, in part using ‘GibInv’ and in part on a ‘trial and error’ basis, and, when necessary, new parameters are derived. Olivine/pyroxene phase relations within such systems and their subsystems are calculated over a wide range of temperatures and pressures and compare very favorably with experimental constraints.

abstract: Primitive arc magmas provide a critical glimpse into the geochemical evolution of subduction zone magmas, as they represent the most unadulterated mantle-derived magmas observed in nature in these tectonic environments and are the precursors of the more abundant andesites and dacites typical in arcs. To date, the study of primitive arc magmas has largely focused on their origins at depth, while significantly less is known about pre-eruptive crustal storage and ascent history. This study examines the crustal storage and ascent history of the Mt. Shasta primitive magnesian andesite (PMA), the demonstrated dominant parent magma for the abundant mixed andesites erupted at Mt. Shasta. Petrographic and geochemical observations of the PMA identify a mid-crustal magma mixing event with a less evolved relative of the PMA recorded in multiple populations of reversely zoned clinopyroxene and orthopyroxene phenocrysts. Prior phase equilibrium experiments and thermobarometric calculations as part of this study suggest the PMA experienced storage, mixing with a less evolved version of itself, and subsequent crystallization at 5kbar and 975°C. Modeling of Fe-Mg interdiffusion between the rims and cores of the reversely-zoned clinopyroxene and orthopyroxenes suggest this mixing, crystallization and subsequent ascent occurred within 10 years, or ~2.9 (+6.5 / -2.5) years, prior to eruption. Ascent from 5kbar or ~15 km, with no meaningful shallower storage, suggests minimum crustal transit rates of ~5 km/year. This rate is comparable to only a couple of other similar types of crustal transit rates (and slower than the much faster, syn-eruptive ascent rates measured through methods like olivine-hosted melt embayment volatile gradients and U-series isotope measurements on other arc magmas). The results of this study help to constrain the pre-eruptive history and ascent rates of hydrous primitive arc magmas, illuminating their magmatic processes during ascent. When combined with geophysical signals of magma movement, mixing to eruption timescales such as this have the power to inform volcanic hazard models for monogenetic, cinder cone eruptions in the Southern Cascades. / Dissertation/Thesis / Masters Thesis Geological Sciences 2019

京都大学 / 新制・課程博士 / 博士(理学) / 甲第24429号 / 理博第4928号 / 新制||理||1704(附属図書館) / 京都大学大学院理学研究科地球惑星科学専攻 / (主査)准教授 三宅 亮, 教授 野口 高明, 教授 下林 典正 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM