Solubility and Diffusivity of Water in Lunar Basalt, and Chemical Zonation in Olivine-Hosted Melt Inclusions

I report the solubility and diffusivity of water in lunar basalt and an iron-free basaltic analogue at 1 atm and 1350 °C. Such parameters are critical for understanding the degassing histories of lunar pyroclastic glasses. Solubility experiments have been conducted over a range of fO₂ conditions from three log units below to five log units above the iron-wüstite buffer (IW) and over a range of pH₂/pH₂O from 0.03 to 24. Quenched experimental glasses were analyzed by Fourier transform infrared spectroscopy (FTIR) and secondary ionization mass spectrometry (SIMS) and were found to contain up to ~420 ppm water. Results demonstrate that, under the conditions of our experiments: (1) hydroxyl is the only H-bearing species detected by FTIR; (2) the solubility of water is proportional to the square root of pH₂O in the furnace atmosphere and is independent of fO₂ and pH₂/pH₂O; (3) the solubility of water is very similar in both melt compositions; (4) the concentration of H₂ in our iron-free experiments is <3 ppm, even at oxygen fugacities as low as IW-2.3 and pH₂/pH₂O as high as 24; and (5) SIMS analyses of water in iron-rich glasses equilibrated under variable fO₂ conditions can be strongly influenced by matrix effects, even when the concentrations of water in the glasses are low. Our results can be used to constrain the entrapment pressure of the lunar melt inclusions of Hauri et al. (2011).

Diffusion experiments were conducted over a range of fO₂ conditions from IW-2.2 to IW+6.7 and over a range of pH₂/pH₂O from nominally zero to ~10. The water concentrations measured in our quenched experimental glasses by SIMS and FTIR vary from a few ppm to ~430 ppm. Water concentration gradients are well described by models in which the diffusivity of water (D^*_water) is assumed to be constant. The relationship between D^*_water and water concentration is well described by a modified speciation model (Ni et al. 2012) in which both molecular water and hydroxyl are allowed to diffuse. The success of this modified speciation model for describing our results suggests that we have resolved the diffusivity of hydroxyl in basaltic melt for the first time. Best-fit values of D^*_water for our experiments on lunar basalt vary within a factor of ~2 over a range of pH₂/pH₂O from 0.007 to 9.7, a range of fO₂ from IW-2.2 to IW+4.9, and a water concentration range from ~80 ppm to ~280 ppm. The relative insensitivity of our best-fit values of D^*_water to variations in pH₂ suggests that H₂ diffusion was not significant during degassing of the lunar glasses of Saal et al. (2008). D^*_water during dehydration and hydration in H₂/CO₂ gas mixtures are approximately the same, which supports an equilibrium boundary condition for these experiments. However, dehydration experiments into CO₂ and CO/CO₂ gas mixtures leave some scope for the importance of kinetics during dehydration into H-free environments. The value of D^*_water chosen by Saal et al. (2008) for modeling the diffusive degassing of the lunar volcanic glasses is within a factor of three of our measured value in our lunar basaltic melt at 1350 °C.

In Chapter 4 of this thesis, I document significant zonation in major, minor, trace, and volatile elements in naturally glassy olivine-hosted melt inclusions from the Siqueiros Fracture Zone and the Galapagos Islands. Components with a higher concentration in the host olivine than in the melt (MgO, FeO, Cr₂O₃, and MnO) are depleted at the edges of the zoned melt inclusions relative to their centers, whereas except for CaO, H₂O, and F, components with a lower concentration in the host olivine than in the melt (Al₂O₃, SiO₂, Na₂O, K₂O, TiO₂, S, and Cl) are enriched near the melt inclusion edges. This zonation is due to formation of an olivine-depleted boundary layer in the adjacent melt in response to cooling and crystallization of olivine on the walls of the melt inclusions concurrent with diffusive propagation of the boundary layer toward the inclusion center.

Concentration profiles of some components in the melt inclusions exhibit multicomponent diffusion effects such as uphill diffusion (CaO, FeO) or slowing of the diffusion of typically rapidly diffusing components (Na₂O, K₂O) by coupling to slow diffusing components such as SiO₂ and Al₂O₃. Concentrations of H2O and F decrease towards the edges of some of the Siqueiros melt inclusions, suggesting either that these components have been lost from the inclusions into the host olivine late in their cooling histories and/or that these components are exhibiting multicomponent diffusion effects.

A model has been developed of the time-dependent evolution of MgO concentration profiles in melt inclusions due to simultaneous depletion of MgO at the inclusion walls due to olivine growth and diffusion of MgO in the melt inclusions in response to this depletion. Observed concentration profiles were fit to this model to constrain their thermal histories. Cooling rates determined by a single-stage linear cooling model are 150–13,000 °C hr^-1 from the liquidus down to ~1000 °C, consistent with previously determined cooling rates for basaltic glasses; compositional trends with melt inclusion size observed in the Siqueiros melt inclusions are described well by this simple single-stage linear cooling model. Despite the overall success of the modeling of MgO concentration profiles using a single-stage cooling history, MgO concentration profiles in some melt inclusions are better fit by a two-stage cooling history with a slower-cooling first stage followed by a faster-cooling second stage; the inferred total duration of cooling from the liquidus down to ~1000 °C is 40 s to just over one hour.

Based on our observations and models, compositions of zoned melt inclusions (even if measured at the centers of the inclusions) will typically have been diffusively fractionated relative to the initially trapped melt; for such inclusions, the initial composition cannot be simply reconstructed based on olivine-addition calculations, so caution should be exercised in application of such reconstructions to correct for post-entrapment crystallization of olivine on inclusion walls. Off-center analyses of a melt inclusion can also give results significantly fractionated relative to simple olivine crystallization.

All melt inclusions from the Siqueiros and Galapagos sample suites exhibit zoning profiles, and this feature may be nearly universal in glassy, olivine-hosted inclusions. If so, zoning profiles in melt inclusions could be widely useful to constrain late-stage syneruptive processes and as natural diffusion experiments.

Generation and evolution of magma beneath the East Pacific Rise: Constraints from U-series disequilibrium and plagioclase-hosted melt inclusions

Mid-ocean ridge basalt (MORB) samples from the East Pacific Rise (EPR 12 degrees 50'N) were analyzed for U-series isotopes and compositions of plagioclase-hosted melt inclusions. The Ra-226 and Th-230 excesses are negatively correlated; the Ra-226 excess is positively correlated with Mg# and Sm/Nd, and is negatively correlated with La/Sm and Fe-8; the Th-230 excess is positively correlated with Fe-8 and La/Sm and is negatively correlated with Mg# and Sm/Nd. Interpretation of these correlations is critical for understanding the magmatic process. There are two models (the dynamic model and the "two-porosity" model) for interpreting these correlations, however, some crucial parameters used in these models are not ascertained. We propose instead a model to explain the U-series isotopic compositions based on the control of melt density variation. For melting either peridotite or the "marble-cake" mantle, the FeOt content, Th-230 excess and La/Sm ratio increases and Sm/Nd decreases with increasing pressure. A deep melt will evolve to a higher density and lower Mg# than a shallow melt, the former corresponds to a long residence time, which lowers the Ra-226 excess significantly. This model is supported by the existence of low Ra-226 excesses and high Th-230 excesses in MORBs having a high Fe-8 content and high density. The positive correlation of Ra-226 excess and magma liquidus temperature implies that the shallow melt is cooled less than the deep melt due to its low density and short residence time. The correlations among Fe-8, Ti-8 and Ca-8/Al-8 in plagioclase-hosted melt inclusions further prove that MORBs are formed from melts having a negative correlation in melting depths and degrees. The negative correlation of Ra-226 excess vs. chemical diversity index (standard deviation of Fe-8, Ti-8 and Ca-8/Al-8) of the melt inclusions is in accordance with the influence of a density-controlled magma residence time. We conclude that the magma density variation exerts significant control on residence time and U-series isotopic compositions. (c) 2010 Elsevier B.V. All rights reserved.

Chemical composition of clinopyroxenes and melt inclusions in clinopyroxenes from rocks of the Malaita Island, Ontong Java Plateau (Pacific Ocean)

The paper is based on new results of melt inclusion studies in minerals. Physicochemical and geochemical parameters of plateau basalt magmatic systems of the Siberian Platform and Ontong Java Plateau (Pacific Ocean) have been established. The studied melts are enriched in Fe. That differs them from magmatic melts of mid-ocean ridges (MOR). A comparative analysis of data on inclusions has shown a similarity of continental and oceanic plateau basalt magmatic systems. They considerably differ from those of MOR and intraplate oceanic islands. Crystallization of oceanic plateau basalts took place at lower temperatures and pressures as compared with similar rocks of the Siberian Platform. The data on inclusions evidence that the melts of the Siberian Platform and the Malaita Island underwent a serious evolution in contrast to magmas of the Nauru Basin that have more stable geochemical parameters. The most fractionated low-temperature high-Fe magmas with elevated contents of trace and rare-earth elements occur in the Malaita Island (Ontong Java Plateau) magmatic system.

Magmatic evolution of topaz-bearing granite stocks within the Wiborg rapakivi granite batholith

This study brings new insights into the magmatic evolution of natural F-enriched peraluminous granitic systems. The Artjärvi, Sääskjärvi and Kymi granite stocks within the 1.64 Ga Wiborg rapakivi granite batholith have been investigated by petrographic, geochemical, experimental and melt inclusion methods. These stocks represent late-stage leucocratic and weakly peraluminous intrusive phases typical of rapakivi granites worldwide. The Artjärvi and Sääskjärvi stocks are multiphase intrusions in which the most evolved phase is topaz granite. The Kymi stock contains topaz throughout and has a well-developed zoned structure, from the rim to the center: stockscheider pegmatite equigranular topaz granite porphyritic topaz granite. Geochemically the topaz granites are enriched in F, Li, Be, Ga, Rb, Sn and Nb and depleted in Mg, Fe, Ti, Ba, Sr, Zr and Eu. The anomalous geochemistry and mineralogy of the topaz granites are essentially magmatic in origin; postmagmatic reactions have only slightly modified the compositions. The Kymi equigranular topaz granite shows the most evolved character, and the topaz granites at Artjärvi and Sääskjärvi resemble the less evolved porphyritic topaz granite of the Kymi stock. Stockscheiders are found at the roof contacts of the Artjärvi and Kymi stocks. The stockscheider at Artjärvi is composed of biotite-rich schlieren and pegmatite layers parallel to the contact. The schlieren layering is considered to have formed by velocity-gradient sorting mechanism parallel to the flow, which led to the accumulation of mafic minerals along the upper contact of the topaz granite. Cooling and contraction of the topaz granite formed fractures parallel to the roof contact and residual pegmatite magmas were injected along the fractures and formed the pegmatite layers. The zoned structure of the Kymi stock is the result of intrusion of highly evolved residual melt from deeper parts of the magma chamber along the fractured contact between the porphyritic granite crystal mush and country rock. The equigranular topaz granite and marginal pegmatite (stockscheider) crystallized from this evolved melt. Phase relations of the Kymi equigranular topaz granite have been investigated utilizing crystallization experiments at 100 to 500 MPa as a function of water activity and F content. Fluorite and topaz can crystallize as liquidus phases in F-rich peraluminous systems, but the F content of the melt should exceed 2.5 - 3.0 wt % to facilitate crystallization of topaz. In peraluminous F-bearing melts containing more than 1 wt % F, topaz and muscovite are expected to be the first F-bearing phases to crystallize at high pressure, whereas fluorite and topaz should crystallize first at low pressure. Overall, the saturation of fluorite and topaz follows the reaction: CaAl2Si2O8 (plagioclase) + 2[AlF3]melt = CaF2 (fluorite) + 2Al2SiO4F2 (topaz). The obtained partition coefficient for F between biotite and glass D(F)Bt/glass is 1.89 to 0.80 (average 1.29) and can be used as an empirical fluormeter to determine the F content of coexisting melts. In order to study the magmatic evolution of the Kymi stock, crystallized melt inclusions in quartz and topaz grains in the porphyritic and the equigranular topaz granites and the marginal pegmatite were rehomogenized and analyzed. The homogenization conditions for the melt inclusions from the granites were 700 °C, 300 MPa, and 24 h, and for melt inclusions from the pegmatite, 700 °C, 100 MPa, and 24/96 h. The majority of the melt inclusions is chemically similar to the bulk rocks (excluding H2O content), but a few melt inclusions in the equigranular granite show clearly higher F and low K2O contents (on average 11.6 wt % F, 0.65 wt % K2O). The melt inclusion compositions indicate coexistence of two melt fractions, a prevailing peraluminous and a very volatile-rich, possibly peralkaline. Combined petrological, experimental and melt inclusion studies of the Kymi equigranular topaz granite indicate that plagioclase was the liquidus phase at nearly water-saturated (fluid-saturated) conditions and that the F content of the melt was at least 2 wt %. The early crystallization of biotite and the presence of muscovite in crystallization experiments at 200 MPa contrasts with the late-stage crystallization of biotite and the absence of muscovite in the equigranular granite, indicating that crystallization pressure may have been lower than 200 MPa for the granite.

辽河盆地西部凹陷深部流体的地球化学特征与成藏效应

The main research area of this thesis is the Western Depression in the Liaohe Basin. Based on the drilling core observation and mud logging data, the features of the mantle–derived fluids and their effects on oil/gas generation in the Western Depression of the Liaohe Basin,was studied with comprehensive methods of volcanic petrology, sediment petrology, fluid geochemistry, sedimentlogy, and structural geology, and use of polarized light microscope, fluorescence microscope, electron microscope, fluid and melt inclusion test, and isotopic test of nature gas etc. The observation of drill cores in study area and other studies reveal that the main passageway of the volcanic eruption in the Cenozoic was the Xibaqian-Gaosheng fault, and the volcanic rocks of each stage were distributed around it. Mantle-derived fluid which affected on oil/gas generation formed later than the volcanic spew and those fluids entered into the depression through the Taian-Dawa fault and the Central fault. The volatile fraction analysis of the melt inclusion reveals the presence of two kinds of mantle fluids; they are hydrogen-rich fluid and carbon dioxide-rich fluid. These the two kinds of fluids were mainly distributed in olivine and pyroxene respectively. The hydrothermal veins development have multiple stages, from high temperature quartz vein to low temperature calcite vein and analcime vein, in which the fluid inclusion extremity component are methane and carbon dioxide, which indicate that when mantle-derived fluids ascended and entered into the basin, most of these fluids interacted with the organic matter in the basin even though some of these entered into atmosphere. The present isotopic test of the nature gas reveals the high 3He/4He value between the region of the Taian-Dawa fault and the Central fault, which also imply the feature of origin in mantle. This phenomenon indicates that the Mesozoic basement faults and the main Cenozoic faults had connected crust and the mantle during the basin evolution, so the mantle derived fluids could enter the basin along those faults. The main source rocks of the ES3 and ES4 members of the Shahejie Formation began to expel hydrocarbon at the end period of the ES1 member of the Shahejie Formation, and reached its peak during the period of the Dongying Formation deposition. During these periods, the mantle derived-fluids entered the basin constantly along the main faults, and supplied lots of hydrogen for hydrocarbon generation. Though the volcanic rocks and the mantle-derived fluids in the Eastern Depression were more developed than in the Western Depression, the source rocks and the deep fluids were not interacted better than the Western Depression because of the affection of structural evolution. In the Eocene, the Eastern Depression did not deposit the ES4 member of the Shahejie Formation, furthermore, the mantle-fluid formed in the Fangshengpao stage escaped to the atmosphere, which confined the later stage hydrocarbon generation capability.

Investigations into the degassing and eruption mechanisms of Nyamuragira volcano, Democratic Republic of the Congo (Africa)

One of two active volcanoes in the western branch of the East African Rift, Nyamuragira (1.408ºS, 29.20ºE; 3058 m) is located in the D.R. Congo. Nyamuragira emits large amounts of SO2 (up to ~1 Mt/day) and erupts low-silica, alkalic lavas, which achieve flow rates of up to ~20 km/hr. The source of the large SO2 emissions and pre-eruptive magma conditions were unknown prior to this study, and 1994-2010 lava volumes were only recently mapped via satellite imagery, mainly due to the region’s political instability. In this study, new olivine-hosted melt inclusion volatile (H2O, CO2, S, Cl, F) and major element data from five historic Nyamuragira eruptions (1912, 1938, 1948, 1986, 2006) are presented. Melt compositions derived from the 1986 and 2006 tephra samples best represent pre-eruptive volatile compositions because these samples contain naturally glassy inclusions that underwent less post-entrapment modification than crystallized inclusions. The total amount of SO2 released from the 1986 (0.04 Mt) and 2006 (0.06 Mt) eruptions are derived using the petrologic method, whereby S contents in melt inclusions are scaled to erupted lava volumes. These amounts are significantly less than satellite-based SO2 emissions for the same eruptions (1986 = ~1 Mt; 2006 = ~2 Mt). Potential explanations for this observation are: 1) accumulation of a vapor phase within the magmatic system that is only released during eruptions, and/or 2) syn-eruptive gas release from unerupted magma. Post-1994 Nyamuragira lava volumes were not available at the beginning of this study. These flows (along with others since 1967) are mapped with Landsat MSS, TM, and ETM+, Hyperion, and ALI satellite data and combined with published flow thicknesses to derive volumes. Satellite remote sensing data was also used to evaluate Nyamuragira SO2 emissions. These results show that the most recent Nyamuragira eruptions injected SO2 into the atmosphere between 15 km (2006 eruption) and 5 km (2010 eruption). This suggests that past effusive basaltic eruptions (e.g., Laki 1783) are capable of similar plume heights that reached the upper troposphere or tropopause, allowing SO2 and resultant aerosols to remain longer in the atmosphere, travel farther around the globe, and affect global climates.

Co-melt fluidised bed granulation of pharmaceutical powders: Improvements in drug bioavailability

This study investigates the use of co-melt fluidised bed granulation for the agglomeration of model pharmaceutical powders, namely, lactose mono-hydrate, PEG 10000, poly-vinyl pyrolidone and ibuprofen as a model drug. Granulation within the co-melt system was found to follow a nucleationâ??steady growthâ??coating regime profile. Using high molecular weight PEG binder, the granulation mechanism and thus the extent of granulation was found to be significantly influenced by binder viscosity. The compression properties of the granulate within the hot fluidised bed were correlated using a novel high temperature experimental procedure. It was found that the fracture stress and fractural modulus of the materials under hot processing conditions were orders of magnitude lower than those measured under ambient conditions. A range of particle velocities within the granulator were considered based on theoretical models. After an initial period of nucleation, the Stokes deformation number analysis indicated that only velocities within the high shear region of the fluidised bed were sufficient to promote significant granule deformation and therefore, coalescence. The data also indicated that larger granules de-fluidised preventing agglomeration by coalescence. Furthermore, experimental data indicated that dissipation of the viscous molten binder to the surface was the most important factor in the latter stages of the granulation process. From a pharmaceutical perspective the inclusion of the model drug, ibuprofen, combined with PVP in the co-melt process proved to be highly significant. It was found that using DSC analysis on the formulations that the decrease in the heat of fusion associated with the melting of ibuprofen within the FHMG systems may be attributed to interaction between PVP and ibuprofen through inter-molecular hydrogen bonding. This interaction decreases the crystallinity of ibuprofen and facilitates solubilisation and bioavailability within the solid matrix.

The manufacture and characterisation of hot-melt extruded enteric tablets

The aim of this highly novel study was to use hot-melt extrusion technology as an alternative process to enteric coating. In so doing, oral dosage forms displaying enteric properties may be produced in a continuous, rapid process, providing significant advantages over traditional pharmaceutical coating technology. Eudragit (R) L100-55, an enteric polymer, was pre-plasticized with triethyl citrate (TEC) and citric acid and subsequently dry-mixed with 5-aminosalicylic acid, a model active pharmaceutical ingredient (API), and an optional gelling agent (PVP (R) K30 or Carbopol (R) 971P). Powder blends were hot-melt extruded as cylinders, cut into tablets and characterised using powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC) and dissolution testing conducted in both pH 1.2 and pH 6.8 buffers. Increasing the concentration of TEC significantly lowered the glass transition temperature (T,) of Eudragit (R) L100-55 and reduced temperatures necessary for extrusion as well as the die pressure. Moreover, citric acid (17% w/w) was shown to act as a solid-state plasticizer. HME tablets showed excellent gastro-resistance, whereas milled extrudates compressed into tablets released more than 10% w/w of the API in acidic media. Drug release from HME tablets was dependent upon the concentration of TEC, the presence of citric acid, PVP K30, and Carbopol (R) 971P in the matrix, and pH of the dissolution media. The inclusion of an optional gelling agent significantly reduced the erosion of the matrix and drug release rate at pH 6.8; however, the enteric properties of the matrix were lost due to the formation of channels within the tablet. Consequently this work is both timely and highly innovative and identifies for the first time a method of producing an enteric matrix tablet using a continuous hot-melt extrusion process.

Characterisation of melt processed nanocomposites of Polyamide 6 subjected to uniaxial-drawing

In this paper, the processing and characterization of Polyamide 6 (PA6) nanocomposites containing graphite nanoplatelets (GNPs) is reported. PA6 nanocomposites were prepared by melt-mixing using an industrial, co-rotating, intermeshing, twin-screw extruder. A bespoke screw configuration was used that was designed in-house to enhance nanoparticle dispersion into a polymer matrix. The effects of nano-filler type (xGnPTM M-5 and xGnPTM C-500), nano-filler content, and extruder screw speed on the bulk properties of the PA6 nanocomposites were investigated. The crystalline structures of PA6 nanocomposites are related to thermal treatment, stress history and the presence of moisture and nanofillers. DSC, Raman and XRD studies show an increase in crystallinity with increasing GNP content and a phase transformation between α-form to γ-form crystals as a result of the heterophase nucleation effect. The effect of uniaxial stretching on PA6 nanocomposites was investigated by drawing specimens heated at temperatures below the melting temperature. DSC and Raman studies on the drawn samples show an increase in yield stress as the GNP content increases due to the strain induced crystallization and γ—β transition during stretching. The rheological response of the nanocomposites resemble that of a ‘pseudo-solid’, rather than a molten liquid, and analysis of the rheological data indicates that a percolation threshold was reached at GNP contents of between 10–15wt%. An increase in tensile modulus of as much as 412% was observed for PA6/C-500 xGnPTM composites, at a filler content of 20wt%. The enhancement of Young’s modulus and yield stress can be attributed to the reinforcing effect of GNPs and their uniform dispersion in the PA6 matrix. The electrical conductivity of the composite also increased with increasing GNP content, with an addition of 15wt% GNP resulting in a 6 order-of-magnitude increase in conductivity. The effects of uniaxial-drawing and the inclusion of multiple nano-filler varieties on the electrical and mechanical properties are currently under investigation.

Melt processing and properties of linear low density polyethylene-graphene nanoplatelet composites

Composites of Linear Low Density Polyethylene (LLDPE) and Graphene Nanoplatelets (GNPs) were processed using a twin screw extruder under different extrusion conditions. The effects of screw speed, feeder speed and GNP content on the electrical, thermal and mechanical properties of composites were investigated. The inclusion of GNPs in the matrix improved the thermal stability and conductivity by 2.7% and 43%, respectively. The electrical conductivity improved from 10−11 to 10−5 S/m at 150 rpm due to the high thermal stability of the GNPs and the formation of phonon and charge carrier networks in the polymer matrix. Higher extruder speeds result in a better distribution of the GNPs in the matrix and a significant increase in thermal stability and thermal conductivity. However, this effect is not significant for the electrical conductivity and tensile strength. The addition of GNPs increased the viscosity of the polymer, which will lead to higher processing power requirements. Increasing the extruder speed led to a reduction in viscosity, which is due to thermal degradation and/or chain scission. Thus, while high speeds result in better dispersions, the speed needs to be optimized to prevent detrimental impacts on the properties.