Evolution of high-pressure mafic granulites and pelitic gneisses from NE Madagascar: Tectonic implications

The occurrence of high-pressure mafic-ultramafic bodies within major shear zones is one of the indicators of paleo-subduction. In mafic granulites of the Andriamena complex (north-eastern Madagascar) we document unusual textures including garnet-clinopyroxene-quartz coronas that formed after the breakdown of orthopyroxene-plagioclase-ilmenite. Textural evidence and isochemical phase diagram calculations in the Na2O-CaO-K2O-FeO-MgO-Al2O3-SiO2-H2O-TiO2 system indicate a pressure-temperature (P-T) evolution from an isothermal (780 degrees C) pressure up to c. 24 kbar to decompression and cooling. Such a P-T trajectory is typically attained in a subduction zone setting where a gabbroic/ultramafic complex is subducted and later exhumed to the present crustal level during oceanic closure and final continental collision. The present results suggest that the presence of such deeply subducted rocks of the Andriamena complex is related to formation of the Betsimisaraka suture. LA-ICPMS U-Pb zircon dating of pelitic gneisses from the Betsimisaraka suture yields low Th/U ratios and protolith ages ranging from 2535 to 2625 Ma. A granitic gneiss from the Alaotra complex yields a zircon crystallization age of ca. 818 Ma and Th/U ratios vary from 1.08 to 2.09. K-Ar dating of muscovite and biotite from biotite-kyanite-sillimanite gneiss and garnet-biotite gneiss yields age of 486 +/- 9 Ma and 459 +/- 9 Ma respectively. We have estimated regional crustal thicknesses in NE Madagascar using a flexural inversion technique, which indicates the presence of an anomalously thick crust (c. 43 km) beneath the Antananarivo block. This result is consistent with the present concept that subduction beneath the Antananarivo block resulted in a more competent and thicker crust. The textural data, thermodynamic model, and geophysical evidence together provide a new insight to the subduction history, crustal thickening and evolution of the high-pressure Andriamena complex and its link to the terminal formation of the Betsimisaraka suture in north-eastern Madagascar. (C) 2015 Elsevier B.V. All rights reserved.

Effect of current density on the microstructure and corrosion properties of plasma electrolytic oxidation (PEO) coatings on AM50 Mg alloy produced in an electrolyte containing clay additives

Plasma electrolytic oxidation coatings were produced on AM50 Mg alloy in alkaline phosphate based electrolyte with montmorillonite clay additives employing current densities of 30, 60, and 120 mA/cm(2). The effect of current density on the microstructure and corrosion properties of the coating was investigated. The clay additives got melted and reactively incorporated into the coating forming an amorphous phase, at all the current densities. However, the coating was predominantly amorphous only at 30 mA/cm(2) and with increasing current density, increasing fractions of crystalline phases were formed. Higher current densities resulted in increased thickness of the coating, but reduced the compactness of the coatings. Electrochemical impedance spectroscopy tests in 0.5 wt.% (0.08 M) and 3.5 wt.% (0.6 M) NaCl solution revealed that the coatings processed at 30 mA/cm(2) exhibited a relatively better initial corrosion resistance owing to its relatively defect-free barrier layer and compactness of the coating. However, the presence of amorphous phases in significant amounts and lack of MgO in the coating resulted in increased rate of dissolution of the coatings and degradation of corrosion resistance. Coatings produced at higher current densities exhibited initial inferior corrosion resistance due to a more defective barrier layer and increased porosity in pore band and outer porous layer. However, the increased amount of crystalline phases and an increased amount of MgO, which resisted dissolution, counterbalanced the negative effects of defective barrier and increased porosity resulting in a relatively lower rate of the degradation of the corrosion resistance. Thus, the corrosion resistance of all the coatings continuously decreased with time and became similar after prolonged immersion in NaCl solution. Increasing current density, therefore, did not prove to be beneficial for the improvement of the corrosion performance of the PEO coatings. (C) 2016 Elsevier B.V. All rights reserved.

Ab initio pair potentials at metal-ceramic interfaces

A systematic approach is proposed to obtain the interfacial interatomic potentials. By inverting ab initio adhesive energy curves for the metal-MgO ceramic interfaces, We derive interfacial potentials between Ag and O2-, Ag and Mg2+, Al and O2-, Al and Mg2+. The interfacial potentials, obtained from this method, demonstrate general features of bondings between metal atoms and ceramic ions.

High-resolution TEM characterization of ZnO core-shell nanowires for dye-sensitized solar cells

Recently ZnO nanowire films have been used in very promising and inexpensive dye-sensitized solar cells (DSSC). It was found that the performance of the devices can be enhanced by functionalising the nanowires with a thin metal oxide coating. This nm-scale shell is believed to tailor the electronic structure of the nanowire, and help the absorption of the dye. Core-shell ZnO nanowire structures are synthesised at low temperature (below 120°C) by consecutive hydrothermal growth steps. Different materials are investigated for the coating, including Mg, Al, Cs and Zr oxides. High resolution TEM is used to characterise the quality of both the nanowire core and the shell, and to monitor the thickness and the degree of crystallisation of the oxide coating. The interface between the nanowire core and the outer shell is investigated in order to understand the adhesion of the coating, and give valuable feedback for the synthesis process. Nanowire films are packaged into dye-sensitised solar cell prototypes; samples coated with ZrO2 and MgO show the largest enhancement in the photocurrent and open-circuit voltage and look very promising for further improvement. © 2010 IOP Publishing Ltd.

Investigations of cohesive zone properties of the interface between metal film and ceramic substrate at nano- and micro-scales

Cohesive zone characterizations of the interface between metal film and ceramic substrate at micro- and nano-scales are performed in the present research. At the nano-scale, a special potential for special material interface (Ag/MgO) is adopted to investigate the interface separation mechanism by using MD simulation, and stress-separation relationship will be obtained. At the micro-scale, peeling experiment is performed for the Al film/Al2O3 substrate system with an adhesive layer at the interface. Adhesive is a mixture of epoxy and polyimide with mass ratio 1:1, by which a brittle cohesive property is obtained. The relationships between energy release rate, the film thickness and the adhesive layer thickness are measured during the steady-state peeling. The experimental result has a similar trend as modeling result for a weak adhesion interface case.

基于跨尺度模型的界面研究

探索和建立不同尺度理论之间的关联模式是科学研究的重要课题，本文基于跨尺度模型着重探讨了金属陶瓷界面的凝聚能和原子结构问题。本文遵循原始Peierls-Nabarro模型的基本思想，提出了一种处理一维界面失配位错组的新方法。在这个推广的Peierls-Nabarro模型中，本文得到了一个简单而且准确的解析解，此解反映了失配位错的核结构、能量与失配度、剪切模量之间的依赖关系。当界面剪切模量较强而失配度较小时，界面的结构可以用一组奇导师Volterra位错来描述，这与一些原子模拟结果一致。采用这一简单的模型，引入第一原理计算得到的数据，此模型可以估算金属陶瓷界面的凝聚能。一维界面失配位错组的Peierls-Nabarro模型还被解析推广描述一大类较宽的位错。在模型中我们引进了一个参数a，通过控制参数a，我们可以系统地改变失配位错芯的宽度、剪切应力的分布和弹性恢复力。随着a增加，位错宽度增加，同时弹性恢复力和失配位错应力的幅度减少。当界面剪切模量强和失配度小时，失配位错的宽度近似线性反比于弹性恢复力的幅度大小。同时当界面剪切模量和失配度固定时，失配能、弹性能和总的界面能随a的增加而减少。界面能和恢复力律形式密切相关，当界面剪切模量弱和失配度大时，这种依赖关系更强。考虑到界面常常是在晶格两个方向都有失配，本文还引进了描述界面周期失配位错的二维广义Peierls-Nabarro模型，使得我们能够定量地研究界面的结构和能量。文中定量分析了广义堆垛能γ面对界面失配位错的结构和能量的影响，分析了位错网中两种位错组的相互作用。当界面剪切模量τ_0变大和失配度f变小时，随着位错核区占整个界面的比重下降，γ面的形状对界面能量和结构影响减弱，结果两种位错组之间的相互作用也减弱。此外γ面的变化还有可能导致位错网结构的转变，也就是导致界面结构的转变。应用此模型，本文还研究了金属－陶瓷Ag/MgO(100)界面，给出了界面的能量和原子结构。文中得出结论：在Ag/MgO(100)界面将会形成{1/2<110>; <110>}类型的位错网。此外由于界面失配位错的形成，Ag/MgO(100)界面凝聚能的理论值900mJ/m~2将减少214mJ/m~2，最终成为686mJ/m~2。基于第一原理赝势平面波的总能计算，文中给出了金属陶瓷Al/MgO(100)界面弛豫和未弛豫时的广义堆垛能面。然后结合第三章发展的广义二维Peierls-Nabarro模型，详细研究了金属陶瓷Al/MgO(100)界面的原子结构和界面能。文中得出的“在Al/MgO(100)界面将会形成{1/2<110>; <110>}类型位错网”的推论，证实了Vellinga等的猜测；文中还预测了凝聚能的理论是在600mJ/m~2（未弛豫情形）和670mJ/m~2（弛豫情形）之间。这个应用表明此方法能够容易地建立连续介质理论和第一原理计算之间的联系，实现理论上的跨尺度。本文最后提出了一种得到界面原子有效对势的反演方法。通过反演金属－MgO陶瓷界面的第一原理计算的凝聚能曲线，我们得到了一些金属原子和陶瓷离子之间的对势，此对势反映了金属陶瓷键合的特性。本文的反演方法提供了通过第一原理计算数据来拟合界面原子对势的一种可行性途径。这种方法可归结为第一类尺度关联理论，即单向的跨尺度关联模式。

Studies of the equation of state and elasticity of mantle minerals

Because the Earth’s upper mantle is inaccessible to us, in order to understand the chemical and physical processes that occur in the Earth’s interior we must rely on both experimental work and computational modeling. This thesis addresses both of these geochemical methods. In the first chapter, I develop an internally consistent comprehensive molar volume model for spinels in the oxide system FeO-MgO-Fe₂O₃-Cr₂O₃-Al₂O₃-TiO₂. The model is compared to the current MELTS spinel model with a demonstration of the impact of the model difference on the estimated spinel-garnet lherzolite transition pressure. In the second chapter, I calibrate a molar volume model for cubic garnets in the system SiO₂-Al₂O₃-TiO₂-Fe₂O₃-Cr₂O₃-FeO-MnO-MgO-CaO-Na₂O. I use the method of singular value analysis to calibrate excess volume of mixing parameters for the garnet model. The implications the model has for the density of the lithospheric mantle are explored. In the third chapter, I discuss the nuclear inelastic X-ray scattering (NRIXS) method, and present analysis of three orthopyroxene samples with different Fe contents. Longitudinal and shear wave velocities, elastic parameters, and other thermodynamic information are extracted from the raw NRIXS data.

Liquid silicate equation of state : using shock waves to understand the properties of the deep Earth

The equations of state (EOS) of several geologically important silicate liquids have been constrained via preheated shock wave techniques. Results on molten Fe₂SiO₄ (fayalite), Mg₂SiO₄ (forsterite), CaFeSi₂O₆ (hedenbergite), an equimolar mixture of CaAl₂Si₂O₈-CaFeSi₂O₆ (anorthite-hedenbergite), and an equimolar mixture of CaAl₂Si₂O₈-CaFeSi₂O₆-CaMgSi₂O₆(anorthite-hedenbergite-diopside) are presented. This work represents the first ever direct EOS measurements of an iron-bearing liquid or of a forsterite liquid at pressures relevant to the deep Earth (> 135 GPa). Additionally, revised EOS for molten CaMgSi₂O₆ (diopside), CaAl₂Si₂O₈ (anorthite), and MgSiO₃ (enstatite), which were previously determined by shock wave methods, are also presented.

The liquid EOS are incorporated into a model, which employs linear mixing of volumes to determine the density of compositionally intermediate liquids in the CaO-MgO-Al₂O₃-SiO₂-FeO major element space. Liquid volumes are calculated for temperature and pressure conditions that are currently present at the core-mantle boundary or that may have occurred during differentiation of a fully molten mantle magma ocean.

The most significant implications of our results include: (1) a magma ocean of either chondrite or peridotite composition is less dense than its first crystallizing solid, which is not conducive to the formation of a basal mantle magma ocean, (2) the ambient mantle cannot produce a partial melt and an equilibrium residue sufficiently dense to form an ultralow velocity zone mush, and (3) due to the compositional dependence of Fe2+ coordination, there is a threshold of Fe concentration (molar X_Fe ≤ 0.06) permitted in a liquid for which its density can still be approximated by linear mixing of end-member volumes.

飞秒激光作用下透明介质材料的反射率演化

利用800nm抽运和400nm探针技术，测量了CaF2和MgO的时间分辨反射率，研究了材料的电子激发和弛豫超快动力学过程。采用耦合动力学模型，探讨了飞秒激光对透明介质材料的激发，以及材料的激发对抽运激光在材料中的传输、分布和反射特性的影响。根据这个理论模型计算了时间分辨反射率的演化，计算结果和实验结果相吻合。研究表明，多光子电离（MPI）和碰撞电离（II）在介质材料的导带电子激发中起着重要的作用。

Chemical and mineralogical characterization of micro-inclusions in diamonds

Secondary-ion mass spectrometry (SIMS), electron probe analysis (EPMA), analytical scanning electron microscopy (SEM) and infrared (IR) spectroscopy were used to determine the chemical composition and the mineralogy of sub-micrometer inclusions in cubic diamonds and in overgrowths (coats) on octahedral diamonds from Zaire, Botswana, and some unknown localities.

The inclusions are sub-micrometer in size. The typical diameter encountered during transmission electron microscope (TEM) examination was 0.1-0.5 µm. The micro-inclusions are sub-rounded and their shape is crystallographically controlled by the diamond. Normally they are not associated with cracks or dislocations and appear to be well isolated within the diamond matrix. The number density of inclusions is highly variable on any scale and may reach 10^(11) inclusions/cm^3 in the most densely populated zones. The total concentration of metal oxides in the diamonds varies between 20 and 1270 ppm (by weight).

SIMS analysis yields the average composition of about 100 inclusions contained in the sputtered volume. Comparison of analyses of different volumes of an individual diamond show roughly uniform composition (typically ±10% relative). The variation among the average compositions of different diamonds is somewhat greater (typically ±30%). Nevertheless, all diamonds exhibit similar characteristics, being rich in water, carbonate, SiO_2, and K_2O, and depleted in MgO. The composition of micro-inclusions in most diamonds vary within the following ranges: SiO_2, 30-53%; K_2O, 12-30%; CaO, 8-19%; FeO, 6-11%; Al_2O_3, 3-6%; MgO, 2-6%; TiO_2, 2-4%; Na_2O, 1-5%; P_2O_5, 1-4%; and Cl, 1-3%. In addition, BaO, 1-4%; SrO, 0.7-1.5%; La_2O_3, 0.1-0.3%; Ce_2O_3, 0.3-0.5%; smaller amounts of other rare-earth elements (REE), as well as Mn, Th, and U were also detected by instrumental neutron activation analysis (INAA). Mg/(Fe+Mg), 0.40-0.62 is low compared with other mantle derived phases; K/ AI ratios of 2-7 are very high, and the chondrite-normalized Ce/Eu ratios of 10-21 are also high, indicating extremely fractionated REE patterns.

SEM analyses indicate that individual inclusions within a single diamond are roughly of similar composition. The average composition of individual inclusions as measured with the SEM is similar to that measured by SIMS. Compositional variations revealed by the SEM are larger than those detected by SIMS and indicate a small variability in the composition of individual inclusions. No compositions of individual inclusions were determined that might correspond to mono-mineralic inclusions.

IR spectra of inclusion- bearing zones exhibit characteristic absorption due to: (1) pure diamonds, (2) nitrogen and hydrogen in the diamond matrix; and (3) mineral phases in the micro-inclusions. Nitrogen concentrations of 500-1100 ppm, typical of the micro-inclusion-bearing zones, are higher than the average nitrogen content of diamonds. Only type IaA centers were detected by IR. A yellow coloration may indicate small concentration of type IB centers.

The absorption due to the micro-inclusions in all diamonds produces similar spectra and indicates the presence of hydrated sheet silicates (most likely, Fe-rich clay minerals), carbonates (most likely calcite), and apatite. Small quantities of molecular CO_2 are also present in most diamonds. Water is probably associated with the silicates but the possibility of its presence as a fluid phase cannot be excluded. Characteristic lines of olivine, pyroxene and garnet were not detected and these phases cannot be significant components of the inclusions. Preliminary quantification of the IR data suggests that water and carbonate account for, on average, 20-40 wt% of the micro-inclusions.

The composition and mineralogy of the micro-inclusions are completely different from those of the more common, larger inclusions of the peridotitic or eclogitic assemblages. Their bulk composition resembles that of potassic magmas, such as kimberlites and lamproites, but is enriched in H_2O, CO_3, K_2O, and incompatible elements, and depleted in MgO.

It is suggested that the composition of the micro-inclusions represents a volatile-rich fluid or a melt trapped by the diamond during its growth. The high content of K, Na, P, and incompatible elements suggests that the trapped material found in the micro-inclusions may represent an effective metasomatizing agent. It may also be possible that fluids of similar composition are responsible for the extreme enrichment of incompatible elements documented in garnet and pyroxene inclusions in diamonds.

The origin of the fluid trapped in the micro-inclusions is still uncertain. It may have been formed by incipient melting of a highly metasomatized mantle rocks. More likely, it is the result of fractional crystallization of a potassic parental magma at depth. In either case, the micro-inclusions document the presence of highly potassic fluids or melts at depths corresponding to the diamond stability field in the upper mantle. The phases presently identified in the inclusions are believed to be the result of closed system reactions at lower pressures.

The Equation of State and Petrogenesis of Komatiite

(1) Equation of State of Komatiite

The equation of state (EOS) of a molten komatiite (27 wt% MgO) was detennined in the 5 to 36 GPa pressure range via shock wave compression from 1550°C and 0 bar. Shock wave velocity, U_S, and particle velocity, U_P, in km/s follow the linear relationship U_S = 3.13(±0.03) + 1.47(±0.03) U_P. Based on a calculated density at 1550°C, 0 bar of 2.745±0.005 glee, this U_S-U_P relationship gives the isentropic bulk modulus K_S = 27.0 ± 0.6 GPa, and its first and second isentropic pressure derivatives, K'_S = 4.9 ± 0.1 and K"_S = -0.109 ± 0.003 GPa^-1.

The calculated liquidus compression curve agrees within error with the static compression results of Agee and Walker [1988a] to 6 GPa. We detennine that olivine (FO₉₄) will be neutrally buoyant in komatiitic melt of the composition we studied near 8.2 GPa. Clinopyroxene would also be neutrally buoyant near this pressure. Liquidus garnet-majorite may be less dense than this komatiitic liquid in the 20-24 GPa interval, however pyropic-garnet and perovskite phases are denser than this komatiitic liquid in their respective liquidus pressure intervals to 36 GPa. Liquidus perovskite may be neutrally buoyant near 70 GPa.

At 40 GPa, the density of shock-compressed molten komatiite would be approximately equal to the calculated density of an equivalent mixture of dense solid oxide components. This observation supports the model of Rigden et al. [1989] for compressibilities of liquid oxide components. Using their theoretical EOS for liquid forsterite and fayalite, we calculate the densities of a spectrum of melts from basaltic through peridotitic that are related to the experimentally studied komatiitic liquid by addition or subtraction of olivine. At low pressure, olivine fractionation lowers the density of basic magmas, but above 14 GPa this trend is reversed. All of these basic to ultrabasic liquids are predicted to have similar densities at 14 GPa, and this density is approximately equal to the bulk (PREM) mantle. This suggests that melts derived from a peridotitic mantle may be inhibited from ascending from depths greater than 400 km.

The EOS of ultrabasic magmas was used to model adiabatic melting in a peridotitic mantle. If komatiites are formed by >15% partial melting of a peridotitic mantle, then komatiites generated by adiabatic melting come from source regions in the lower transition zone (≈500-670 km) or the lower mantle (>670 km). The great depth of incipient melting implied by this model, and the melt density constraint mentioned above, suggest that komatiitic volcanism may be gravitationally hindered. Although komatiitic magmas are thought to separate from their coexisting crystals at a temperature =200°C greater than that for modern MORBs, their ultimate sources are predicted to be diapirs that, if adiabatically decompressed from initially solid mantle, were more than 700°C hotter than the sources of MORBs and derived from great depth.

We considered the evolution of an initially molten mantle, i.e., a magma ocean. Our model considers the thermal structure of the magma ocean, density constraints on crystal segregation, and approximate phase relationships for a nominally chondritic mantle. Crystallization will begin at the core-mantle boundary. Perovskite buoyancy at > 70 GPa may lead to a compositionally stratified lower mantle with iron-enriched mangesiowiistite content increasing with depth. The upper mantle may be depleted in perovskite components. Olivine neutral buoyancy may lead to the formation of a dunite septum in the upper mantle, partitioning the ocean into upper and lower reservoirs, but this septum must be permeable.

(2) Viscosity Measurement with Shock Waves

We have examined in detail the analytical method for measuring shear viscosity from the decay of perturbations on a corrugated shock front The relevance of initial conditions, finite shock amplitude, bulk viscosity, and the sensitivity of the measurements to the shock boundary conditions are discussed. The validity of the viscous perturbation approach is examined by numerically solving the second-order Navier-Stokes equations. These numerical experiments indicate that shock instabilities may occur even when the Kontorovich-D'yakov stability criteria are satisfied. The experimental results for water at 15 GPa are discussed, and it is suggested that the large effective viscosity determined by this method may reflect the existence of ice VII on the Rayleigh path of the Hugoniot This interpretation reconciles the experimental results with estimates and measurements obtained by other means, and is consistent with the relationship of the Hugoniot with the phase diagram for water. Sound waves are generated at 4.8 MHz at in the water experiments at 15 GPa. The existence of anelastic absorption modes near this frequency would also lead to large effective viscosity estimates.

(3) Equation of State of Molybdenum at 1400°C

Shock compression data to 96 GPa for pure molybdenum, initially heated to 1400°C, are presented. Finite strain analysis of the data gives a bulk modulus at 1400°C, K'_S. of 244±2 GPa and its pressure derivative, K'_OS of 4. A fit of shock velocity to particle velocity gives the coefficients of U_S = C_O+S U_P to be C_O = 4.77±0.06 km/s and S = 1.43±0.05. From the zero pressure sound speed, C_O, a bulk modulus of 232±6 GPa is calculated that is consistent with extrapolation of ultrasonic elasticity measurements. The temperature derivative of the bulk modulus at zero pressure, θK_OSθT|_P, is approximately -0.012 GPa/K. A thermodynamic model is used to show that the thermodynamic Grüneisen parameter is proportional to the density and independent of temperature. The Mie-Grüneisen equation of state adequately describes the high temperature behavior of molybdenum under the present range of shock loading conditions.

掺镁近化学计量比LiTaO3晶体的生长及光学性能

在同成分LiTaO3熔体中掺入一定剂量的K2O,采用顶部籽晶提拉法生长掺镁近化学计量比LiTaO3晶体。对晶体分别进行光谱分析,畴结构和抗光损伤阈值的测定。结果表明：与同成分掺镁LiTaO3晶体相比较,其紫外吸收边出现明显蓝移,红外吸收峰变弱。腐蚀晶片的晶相显微镜观察结果表明：掺镁近化学剂量比晶体的畴结构是较为规则的六边形;晶体的抗光致散射能力明显提高。

Electrochromism accompanying ferroelectric domain inversion in congruent RuO2 : LiNbO3 crystal

Electrochromic phenomena accompanying the ferroelectric domain inversion in congruent RuO2-doped z-cut LiNbO3 crystals at room temperature are observed in experiments. During the electric poling process, the electrochromism accompanies the ferroelectric domain inversion simultaneously in the same poled area. The electrochromism is completely reversible when the domain is inverted from the reverse direction. The influences of electric field and annealing conditions on domain inversion and electrochromism are also discussed. We propose the reasonable assumption that charge redistribution within the crystal structure caused by domain inversion is the source for electrochemically oxidation and reduction of Ru ion to produce the electrochromic effect. (c) 2005 Optical Society of America.

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.

Produção de biodiesel a partir da alcoólise do óleo de palma

No presente trabalho foi investigada a produção de biodiesel a partir da alcoólise do óleo de palma catalisada por lipase imobilizada comercial. O efeito da razão molar de álcool:óleo, da forma de adição do álcool (única e escalonada), da temperatura de reação, da concentração de enzima, do tipo de álcool (metanol e etanol), do tipo de enzima e da reutilização da enzima no rendimento final de reação foi avaliado. As reações conduzidas com etanol apresentaram rendimentos superiores aos obtidos com o emprego de metanol devido à maior desativação da lipase pelo álcool de menor número de átomos de carbono. O maior rendimento em biodiesel (54%) foi obtido empregando razão molar de álcool:óleo de 3:1, com adição escalonada de etanol (0, 30 e 60 minutos), 9% (m/m) de Lipozyme TL IM a 50C. Não foi possível recuperar a lipase ao final das reações, pois a matriz de imobilização se solubilizou no meio. Além disso, para comparação, foi investigada a utilização das lipases comerciais imobilizadas Lipozyme RM IM e Novozym 435 e dos catalisadores químicos KOH, MgO e La2O3. O rendimento em biodiesel nas reações catalisadas pelas lipases foi maior do que os obtidos com catalisadores químicos. A menor eficiência dos catalisadores químicos pode ser justificada pelo alto índice de acidez do óleo de palma (6,26 mg KOH.g-1) que promove o consumo do catalisador (KOH), devido à neutralização dos ácidos graxos livres presentes no óleo, e o bloqueio dos sítios ativos dos catalisadores químicos sólidos devido à adsorção dos ácidos graxos nestes sítios