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.

Kimberlite hosts two populations of olivine that are distinguished on the basis of grain size and morphology; the populations are commonly described genetically as xenocrysts and phenocrysts. Recent studies of zoning patterns in kimberlitic olivine phenocrysts have cast doubt on the actual origins of the smaller olivine crystals. Here, we elucidate the nature and origins of the textural and chemical zonation that characterize both populations of olivine. Specifically, we show that both olivine-I and olivine-II feature chemically distinct overgrowths resulting from magmatic crystallization on pre-existing olivine xenocrysts. These results suggest that the total volume of olivine crystallized during transport is substantially lower (≤5%) than commonly assumed (e.g. ~25%), and that crystallization is dominantly heterogeneous. This reduces estimates of the Mg# in primitive kimberlite melt to more closely reconcile with measured phenocryst compositions. Several additional textures are observed in olivine, and include: sealed cracks, healed cracks, phases trapping in cracks, rounded grains, overgrowths and phase trapping in overgrowths. These features record processes that operate in kimberlite during ascent, and from these features we create a summary model for kimberlite ascent: • Olivine is incorporated into kimberlitic melts at great depths as peridotitic mantle xenoliths. • Shortly after the incorporation of these xenocrysts the tensile strength of the crystals within xenoliths is reached at a minimum of 20 km from its source. Disaggregation of mantle xenoliths producing xenocrysts is facilitated by expansion of the minerals within the xenoliths. • The void space produced by the failure of the crystals is filled with melt and crystals consisting of primary carbonate (high-Sr), chromite and spinel crystals. The carbonate later crystallizes to produce sealed fractures. • Subsequent decompression causes cracks that are smaller than the sealed cracks and are preserved as healed cracks that crosscut sealed cracks. • Mechanical rounding of the xenocrysts post-dates, and/or occurs contemporaneously with decompression events that cause cracking. • Saturation of olivine produces rounded overgrowths on large xenocrysts, euhedral overgrowths on smaller xenocrysts, and a volumetrically minor population of olivine phenocrysts. Olivine growth traps fluid, solid and melt inclusions. Calculations based on these relationships suggest that the melt saturates with olivine at a maximum depth of 20 km and a minimum depth of 7 km.

Kimberlite hosts two populations of olivine that are distinguished on the basis of grain size and morphology; the populations are commonly described genetically as xenocrysts and phenocrysts. Recent studies of zoning patterns in kimberlitic olivine phenocrysts have cast doubt on the actual origins of the smaller olivine crystals. Here, we elucidate the nature and origins of the textural and chemical zonation that characterize both populations of olivine. Specifically, we show that both olivine-I and olivine-II feature chemically distinct overgrowths resulting from magmatic crystallization on pre-existing olivine xenocrysts. These results suggest that the total volume of olivine crystallized during transport is substantially lower (≤5%) than commonly assumed (e.g. ~25%), and that crystallization is dominantly heterogeneous. This reduces estimates of the Mg# in primitive kimberlite melt to more closely reconcile with measured phenocryst compositions. Several additional textures are observed in olivine, and include: sealed cracks, healed cracks, phases trapping in cracks, rounded grains, overgrowths and phase trapping in overgrowths. These features record processes that operate in kimberlite during ascent, and from these features we create a summary model for kimberlite ascent: • Olivine is incorporated into kimberlitic melts at great depths as peridotitic mantle xenoliths. • Shortly after the incorporation of these xenocrysts the tensile strength of the crystals within xenoliths is reached at a minimum of 20 km from its source. Disaggregation of mantle xenoliths producing xenocrysts is facilitated by expansion of the minerals within the xenoliths. • The void space produced by the failure of the crystals is filled with melt and crystals consisting of primary carbonate (high-Sr), chromite and spinel crystals. The carbonate later crystallizes to produce sealed fractures. • Subsequent decompression causes cracks that are smaller than the sealed cracks and are preserved as healed cracks that crosscut sealed cracks. • Mechanical rounding of the xenocrysts post-dates, and/or occurs contemporaneously with decompression events that cause cracking. • Saturation of olivine produces rounded overgrowths on large xenocrysts, euhedral overgrowths on smaller xenocrysts, and a volumetrically minor population of olivine phenocrysts. Olivine growth traps fluid, solid and melt inclusions. Calculations based on these relationships suggest that the melt saturates with olivine at a maximum depth of 20 km and a minimum depth of 7 km.

Volatiles are fundamental to many aspects of kimberlite magmatism. However, the volatile compositions and concentrations are poorly defined. Enrichment of H in kimberlitic olivines, many of which are xenocrysts, suggests high water content, but the extent to which H exchanges between these xenocrysts and kimberlite magmas remains unclear. This study investigates zonation of H in kimberlite-hosted xenolith and macrocrystic olivines using Fourier transform infrared spectroscopy to constrain the extent of re-equilibration. Data show that, depending on locality, xenolith olivines exhibit either no H-zonation, or substantial H-depletion in their rims. Macrocrysts feature similar trends to xenolith olivines from the same intrusion. In terms of the rim:core ratio of H, strongly zoned olivines average ~0.5, whereas poorly zoned olivines average at ~0.9 (macrocrysts) or 1.0 (xenolith olivines). Locality-specific H-zonation could result from different magmatic thermal regimes, water concentrations, or ascent durations. If the magmas that contained weakly zoned olivines were anhydrous, their restricted zoning requires ascent durations (< 20 min at 1100 °C) that are considerably shorter than published estimates (~1-24 hr at 1100 °C). These findings suggest that elevated magmatic water concentrations minimized loss of H from olivine in these kimberlites, showing that non-equilibrated xenocrysts could indirectly record high water concentrations in the form of weak H-zonation. Strong H-depletion patterns in olivines from other kimberlites may reflect lower initial magmatic water concentrations, or loss of fluid to country rocks. Future studies could compare H-zonation to temperature and ascent rate estimates, and field relationships to better elucidate the causes of locality-specific H-zonation. An apparent correlation between diamond grade and H-zonation warrants further investigation. / This thesis includes an Electronic Appendix, available at http://dalspace.library.dal.ca

Abrasive Waterjet cutting (AWJ) presents many advantages over competing machining techniques, but several issues are related to the high volume of materials (and in particular of abrasive) used in the process. In this study, the environmental impact of the material flows in the abrasive waterjet industry has been analyzed adopting a life cycle perspective in order to individuate which phases place the largest burden on the environment. Moreover, three alternative abrasives (crushed rock, recycled glass and synthetic abrasive) and three disposal practices (in-site recycling, off-site recycling and recycling as construction material) have been also evaluated to estimate the benefits that can be achieved if these could be used in place of garnet abrasives and landfilling. The transportation of the abrasive resulted to be the phase that has the largest influence in every case and thus should be reduced as much as possible. For what concerns the alternative options, the usage of recycled glass and the in-site recycling of the abrasive were the two alternatives with the best environmental performances. However, crushed rock could be the best option for what concerns the global warming potential if carbon sequestration due to carbonation of silicate rocks is taken into account. Off-site recycling and recycling as construction material are good options only if the transportation to the recycling site can be reduced. Synthetic abrasive are instead found to have a much larger impact compared to every other alternative examined.

An experimental study of the partitioning of aluminum between olivine and spine] was carried out at 100 kPa over the temperature range 1250-1450°C at an oxygen fugacity 1.8 log units below the quartz-fayalite-magnetite buffer in basaltic starting compositions. The partitioning is temperature sensitive and experimental data can be fitted to the relation: T.al (K) = -10500/ {ln([Al2O3]ol/[Al2O3]SP) - 0.98 *(Cr#-sp-0.5) -- 0.75J where [Al2O3]° and [Al2O3] se are concentrations of Al2O3 in olivine and spinel (wt%), and Cr#-sp is Crl(Cr+A1+Fe3+) in spinel. This thermometer is calibrated for olivine with MgI(Mg+Fe) between 0.87 and 0.93, and spine] with Crl(Cr+Al+Fe3+) between 0.07 and 0.63 and Fe 3+/(Cr+Al+Fe3+) between 0.02 and 0.05. and it reproduces experimental conditions to ±20°C. This thermometer generally yields temperatures lower than the two pyroxene thermometer when applied to natural mantle peridotites. The difference may be caused by inaccuracy in both thermometers or by faster Al diffusion in olivine than Ca diffusion in the pyroxenes. Preliminary investigations of the potential of Cr and Si exchange between olivine and spinel as further geothermobarometers are also presented.

Geochemical processes involving the interaction of fluids and minerals occur in nearly every environment on the surface and in the crust of the Earth. The variety of fluid–mineral processes on the Earth is quite diverse, and these various processes can occur under a large range of geochemical conditions. Aqueous dissolution and alteration, hydration, protonation, solution–precipitation, diffusion, and fluid and isotope exchange are among the many fluid–mineral interaction processes that contribute to the overall cycling of elements on Earth. This dissertation uses analog experiments to examine fluid­–mineral interaction processes found in different geological environments and under a range of environmental conditions. The first part of this dissertation examines the reactive and diffusive exchange of oxygen isotopes that results from performing a dolomite breakdown experiment under a temperature, pressure, and fluid condition analogous to a contact metamorphic environment. The second two parts of the dissertation involve the development of new methods for the growth of nanocrystalline fayalite and intermediate composition olivine. The final two parts of this dissertation focus on the interaction of olivine with either H2O or acidic solutions (0.005 M H2SO4 or 0.01 M HCl) at low temperature and pressure. The first of these two parts experimentally uses different surface area olivine powders that are reacted with low pH fluids in non-buffered, closed system experiments where pH and solution composition are allowed to change. The second of these two parts uses various analytical techniques that can examines changes to the surfaces of olivine single crystals at the nanoscale resulting from experiments performed under environmental conditions where the fluid–mineral interaction transitions from dissolution at low temperature and pressure to alteration at moderate temperature and pressure. Though the individual projects contained within this dissertation are varied, they share the common theme of using experiments to examine fluid­–mineral interaction processes.

Thesis (Ph.D.)--Wake Forest University. Dept. of Physics, 2006. / Vita. Includes bibliographical references (leaves 90-95)

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 &amp; Hofmann 2017).

abstract: The present work covers two distinct microanalytical studies that address issues in planetary materials: (1) Genesis Na and K solar wind (SW) measurements, and (2) the effect of water on high-pressure olivine phase transformations. NASA’s Genesis mission collected SW samples for terrestrial analysis to create a baseline of solar chemical abundances based on direct measurement of solar material. Traditionally, solar abundances are estimated using spectroscopic or meteoritic data. This study measured bulk SW Na and K in two different Genesis SW collector materials (diamond-like carbon (DlC) and silicon) for comparison with these other solar references. Novel techniques were developed for Genesis DlC analysis. Solar wind Na fluence measurements derived from backside depth profiling are generally lower in DlC than Si, despite the use of internal standards. Nevertheless, relative to Mg, the average SW Na and K abundances measured in Genesis wafers are in agreement with solar photospheric and CI chondrite abundances, and with other SW elements with low first ionization potential (within error). The average Genesis SW Na and K fluences are 1.01e11 (+9e09, -2e10) atoms/cm2 and 5.1e09 (+8e08, -8e08) atoms/cm2, respectively. The errors reflect average systematic errors. Results have implications for (1) SW formation models, (2) cosmochemistry based on solar material rather than photospheric measurements or meteorites, and (3) the accurate measurement of solar wind ion abundances in Genesis collectors, particularly DlC and Si. Deep focus earthquakes have been attributed to rapid transformation of metastable olivine within the mantle transition zone (MTZ). However, the presence of H2O acts to overcome metastability, promoting phase transformation in olivine, so olivine must be relatively anhydrous (<75 ppmw) to remain metastable to depth. A microtextural analysis of olivine phase transformation products was conducted to test the feasibility for subducting olivine to persist metastably to the MTZ. Transformation (as intracrystalline or rim nucleation) shifts from ringwoodite to ringwoodite-wadsleyite nucleation with decreasing H2O content within olivine grains. To provide accurate predictions for olivine metastability at depth, olivine transformation models must reflect how changing H2O distributions lead to complex changes in strain and reaction rates within different parts of a transforming olivine grain. / Dissertation/Thesis / Doctoral Dissertation Geological Sciences 2015