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Pando, K. M.

Publications and source records attributed to Pando, K. M..

Oxygen Buffering in High Pressure Solid Media Assemblies: New Approach Enabling Study of fO2 from IW-4 to IW+4.5

Oxygen fugacity is an intensive parameter that controls some fundamental chemical and physical properties in planetary materials. In terrestrial magmas high fO2 promotes magnetite stability and low fO2 causes Fe-enrichment due to magnetite suppression. In lunar and asteroidal basalts, low fO2 can allow metal to be stable. Experimental studies will therefore be most useful if they are done at a specific and relevant fO2 for the samples under consideration. Control of fO2 in the solid media apparatus (piston cylinder multi-anvil) has relied on either sliding sensors or graphite capsule buffering, which are of limited application to the wide range of fO2 recorded in planetary or astromaterials. Here we describe a new approach that allows fO2 to be specified across a wide range of values relevant to natural samples.

Righter, K.↗

Melting of the Primitive Mercurian Mantle, Insights into the Origin of Its Surface Composition

Recent findings of the MESSENGER mission on Mercury have brought new evidence for its reducing nature, widespread volcanism and surface compositional heteregeneity. MESSENGER also provided major elemental ratios of its surface that can be used to infer large-scale differentiation processes and the thermal history of the planet. Mercury is known as being very reduced, with very low Fe-content and high S and alkali contents on its surface. Its bulk composition is therefore likely close to EH enstatite chondrites. In order to elucidate the origin of the chemical diversity of Mercury's surface, we determined the melting properties of EH enstatite chondrites, at pressures between 1 bar and 3 GPa and oxygen fugacity of IW-3 to IW-5, using piston-cylinder experiments, combined with a previous study on EH4 melting at 1 bar. We found that the presence of Ca-rich sulfide melts induces significant decrease of Ca-content in silicate melts at low pressure and low degree of melting (F). Also at pressures lower than 3 GPa, the SiO2-content decreases with F, while it increases at 3 GPa. This is likely due to the chemical composition of the bulk silicate which has a (Mg+Fe+Ca)/Si ratio very close to 1 and to the change from incongruent to congruent melting of enstatite. We then tested whether the various chemical compositions of Mercury's surface can result from mixing between two melting products of EH chondrites. We found that the majority of the geochemical provinces of Mercury's surface can be explained by mixing of two melts, with the exception of the High-Al plains that require an Al-rich source. Our findings indicate that Mercury's surface could have been produced by polybaric melting of a relatively primitive mantle.

Boujibar, A.↗

The Origin of Mercury's Surface Composition, an Experimental Investigation

Introduction: Results from MESSENGER spacecraft have confirmed the reduced nature of Mercury, based on its high core/mantle ratio and its FeO-poor and S-rich surface. Moreover, high resolution images revealed large volcanic plains and abundant pyroclastic deposits, suggesting major melting stages of the Mercurian mantle. In addition, MESSENGER has provided the most precise data to date on major elemental compositions of Mercury's surface. These results revealed considerable chemical heterogeneities that suggested several stages of differentiation and re-melting processes. This interpretation was challenged by our experimental previous study, which showed a similar compositional variation in the melting products of enstatite chondrites, which are a possible Mercury analogue. However, these experimental melts were obtained over a limited range of pressure (1 bar to 1 gigapascal) and were not compared to the most recent elemental maps. Therefore, here we extend the experimental dataset to higher pressures and perform a more quantitative comparison with Mercury's surface compositions measured by MESSENGER. In particular, we test whether these chemical heterogeneities result from mixing between polybaric melts. Our experiments and models show that the majority of chemical diversity of Mercury's surface can result from melting of a primitive mantle compositionally similar to enstatite chondrites in composition at various depths and degrees of melting. The high-Mg region's composition is reproduced by melting at high pressure (3 gigapascals) (Tab. 1), which is consistent with previous interpretation as being a large degraded impact basin based on its low elevation and thin average crust. While low-Mg NVP (North Volcanic Plains) are the result of melting at low pressure (1 bar), intermediate-Mg NVP, Caloris Basin and Rachmaninoff result from mixing of a high-pressure (3 gigapascals) and low-pressure components (1 bar for Rachmaninoff and 1 gigapascal for the other regions) (Tab. 1). Moreover, all compositions suggest mixing between low and high degree melts that indicate important differentiation processes.

Boujibar, A.↗

The Combined Strength of Thermodynamics and Comparative Planetology: Application of Activity Models to Core Formation in Terrestrial Bodies

Recent models for accretion of terrestrial bodies involve metal-silicate equilibrium as the metallic core formed during growth. Most elements considered are either refractory or well studied elements for which effects of pressure, temperature, oxygen fugacity, and metallic liquid composition are well known. There are a large number of elements that are both siderophile and volatile, whose fate in such models is unknown, largely due to a lack of data at comparable conditions and com-positions (FeNi core with light elements such as S, C, Si, and O). We have focused on Ge, In, As, Sb and determined the effect of Si and C on metal-silicate partitioning, and developed a thermo-dynamic model that allows application of these new data to a wide range of planetary bodies. New experiments: We have previously carried out experiments with FeSi metallic liquid at C-saturated conditions at 1600 and 1800 C [4]. In a new series of experiments we investigate the effect of Si in carbon-free systems at 1600 C for comparison. Experiments were carried out at 1 GPa in MgO capsules using the same basaltic starting composition as in previous studies. The MgO capsule reacts with the silicate melt to form more MgO-rich liquids that have 22-26 wt% MgO. Experimental met-als and silicates were analyzed using a combination of electron microprobe analysis and laser ablation ICP-MS. Results: The new results can be interpreted by considering Ge as an example, in the simple exchange equilibrium Fe + GeO = FeO + Ge, where the equilibrium constant Kd can be examined as a function of Si content of the metal. The slope of lnKd vs. (1-XSi) for this new series allows derivation of the epsilon interaction parameter for each of these four elements and Si (both C-saturated and C-free).All four elements have positive epsilon values, indicating that Si causes a decrease in the partition coefficients; values are 6.6, 6.5, 27.8 and 25.2 for In, Ge, As, and Sb, respectively, at 1 GPa and 1600 C. As an example of how large the effect of Si can be, these epsilon values correspond to activity coefficients (gamma) for As of 0.01 when XSi = 0, and up to gamma = 23 when XSi = 0.2. Combining these new results with previous determinations [5,6] of epsilon parameters for S and C for these elements allows us calculate activity of Ge, In, As, and Sb in Fe-Ni-Si-S-C-O metallic liquids. We apply this new model to sever-al terrestrial bodies such as Earth (Si-rich core), Mars (S-rich core), Moon (S-, C-, and Si-poor core), and Vesta, and examine the resulting core and mantle concentrations of these elements. Mantle concentrations of these four elements are well explained for Earth and Mars in models that call for mid-mantle equilibration between Si-bearing and S-bearing FeNi cores, respectively. Modeling results for the Moon and Vesta will also be presented.

Righter, K.↗

Origin of Volatiles in Earth: Indigenous Versus Exogenous Sources Based on Highly Siderophile, Volatile Siderophile, and Light Volatile Elements

Origin of Earth's volatiles has traditionally been ascribed to late accretion of material after major differentiation events - chondrites, comets, ice or other exogenous sources. A competing theory is that the Earth accreted its volatiles as it was built, thus water and other building blocks were present early and during differentiation and core formation (indigenous). Here we discuss geochemical evidence from three groups of elements that suggests Earth's volatiles were acquired during accretion and did not require additional sources after differentiation.

Righter, K.↗