Experimental investigation into lunar melt density and compressibility : the role of titanium

This study focuses on determining the density and compressibility of four lunar picritic glasses as a function of TiO2 content from 0-11 GPa and 1748-2473 K (1475-2200°C). These glasses are hypothesized to have quenched rapidly as glass beads during lunar fire fountain eruptions. The lunar glass beads have distinctive colors that correspond to TiO2 content. The glasses of interest for this study are the Apollo 15 green glass Type C (A15C) which has a TiO2 content of 0.26 wt%, the Apollo 14 yellow glass (A14Y) which has a TiO2 content of 4.58 wt%, the Apollo 17 orange glass 74220-type (A17O) which has a TiO2 content of 9.12 wt%, and the Apollo 14 black glass (A14B) which has the highest TiO2 content with 16.40 wt%. These glasses are believed to represent primary, unfractionated melts making them excellent candidates for experimental studies into lunar basalt density and eruptability during partial melting of the lunar mantle. We performed sink-float experiments on these lunar glass compositions using a piston-cylinder apparatus (P \u3c 2 GPa) and Walker-style multi-anvil device (P \u3e 2 GPa) in order to bracket the density of these melts. We report new sink-float data for A15C, A14Y, and A17O. We find that with increasing pressure, the melts with less TiO2 are more compressible than high TiO2 melts. This causes the melt with the most TiO2 (A14B) to be the least dense at higher pressures, a complete reversal of what is seen at lower pressures. This change in density and compressibility is attributed to the change from [IV]Ti4+ to [VI]Ti4+ in the melt structure for melts with high TiO2 contents. We have identified density crossovers between these melts and their equilibrium olivines and pyroxenes, and show that these glasses, with the exception of A17O, should be able to rise to the surface as a result of buoyancy forces alone. For the eruption of A17O, we must call upon the rising diapir model of Hess (1991) to explain its eruptability

Experimental Investigation into the Thermal and Magmatic Evolution of Mercury

During the time that the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft was in orbit around the innermost planet, new and exciting results regarding the planets structure, chemical makeup, and diverse surface were revealed, confirming that Mercury is a geochemical endmember among the terrestrial planets. Data from this mission, more specifically data from the X-Ray Spectrometer and Gamma-Ray Spectrometer onboard MESSENGER, has been used to provide insight into the thermal and magmatic evolution of Mercury. This dissertation consists of five chapters that, as a whole, have substantially increased our knowledge about Mercury through a high pressure and high temperature experimental investigation. First, we identified nine distinct geochemical regions that have characteristic major element compositions. We computed silicate and sulfide mineralogy of these regions and petrologically classified them according to IUGS specifications. The diversity of the rocks and minerals on Mercury was then compared to other planetary bodies revealing the wide range in diversity of the mercurian surface. Second, we conducted sink-float experiments on a melt composition similar to the composition of the largest volcanic field on the planet to provide insight into crust formation on Mercury. These results suggested a primary floatation crust composed of graphite is possible given a magma ocean event on Mercury. Third, we experimentally determined the phase assemblages associated with the largest volcanic field on the planet. From this data we were able to provide insight into eruption scenarios that produced the northern volcanic plains on Mercury. Fourth, we determined the sulfide concentration at sulfide saturation in mercurian-like melts by conducting sulfide solubility experiments on a synthetic rock composition matching the northern volcanic plains. These results indicated that the high amounts of sulfur on the surface of Mercury measured by MESSENGER are a direct consequence of the low oxygen fugacity of the planet, which allowed transport of S towards the surface in reducing melts which have a higher carrying capacity for S than oxidized melts. Finally, we investigated the carbon concentration at graphite saturation in Fe-rich metals with various amounts of Si to determine the amount of C that would be soluble in the mercurian core as a function of core composition and temperature. The results of this dissertation provide important information regarding the evolution of Mercury from its primary magma ocean event to the current state of the planet

Experimental Insights into the Geochemistry of Mercury

With the recent estimate of Mercury's surface composition from the X-Ray Spectrometer and Gamma-Ray Spectrometer that were onboard NASA's MErcury Surface, Space ENvironment, Geochemistry and Ranging (MESSENGER) spacecraft, we now have our first opportunity to directly investigate the compositions of lavas from the planet Mercury and indirectly investigate the chemical make-up of its interior. Results from MESSENGER showed exotic surface compositions with more than 3 wt% sulfur in some lavas and relatively low amounts of iron (less than 3 wt%) across the surface. These striking features are consistent with magmatism occurring under highly reducing conditions which has an impact on the thermal and chemical evolution of a planetary body. Here we'll explore the geochemical evolution of Mercury through a series of experimental studies and discuss the implications of low oxygen fugacity on elemental behavior and magmatic processes

Hot Rocks! Near-Infrared Reflectances (and Emissivities) or Rocks at Venus Surface Temperatures

Venus surface can be viewed in emission through a few near-infrared (NIR) spectral windows (1 m) in its relatively opaque atmosphere [1]. Venus surface shows NIR emissivities that correlate with surface geology [2-4], and these emissivity variations are interpreted as differences in surface rock type (mafic vs. silicic) and/or extent of weathering (Fe2+ silicates vs. Fe3+-oxide-coated). To understand and quantify the observed variations in NIR emissivity, high-temperature (T) emissivity can be measured directly [5,6]. For example, emissivities of basalts in the wavelength range 0.85 1.2 m are ~0.95 [5-8]. This can be tested by measureing reflectance, because Kirchoffs Law holds that emissivity (e) = 1 reflectance (r). The r of basalt in the NIR is ~0.05 [o] consistent with a NIR e of ~0.95 [5-8]. High-T NIR es of silicic igneous rocks (granitic, rhyolite) have been reported to be 0.8-0.9 [5,6], which is inconsistent with r values of 0.3-0.8 of such rocks at 25C [9,10]. However, these measurements have been updated [7,8] and are consistent with the results here (see below and Fig. 3)

Apatite-Melt Partitioning at 1 Bar: An Assessment of Apatite-Melt Exchange Equilibria Resulting from Non-Ideal Mixing of F and Cl in Apatite

The mineral apatite [Ca5(PO4)3(F,Cl,OH)] is present in a wide range of planetary materials. Due to the presence of volatiles within its crystal structure (X-site), many recent studies have attempted to use apatite to constrain the volatile contents of planetary magmas and mantle sources. In order to use the volatile contents of apatite to precisely determine the abundances of volatiles in coexisting silicate melt or fluids, thermodynamic models for the apatite solid solution and for the apatite components in multi-component silicate melts and fluids are required. Although some thermodynamic models for apatite have been developed, they are incomplete. Furthermore, no mixing model is available for all of the apatite components in silicate melts or fluids, especially for F and Cl components. Several experimental studies have investigated the apatite-melt and apatite-fluid partitioning behavior of F, Cl, and OH in terrestrial and planetary systems, which have determined that apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, McCubbin et al. recently reported that the exchange coefficients may vary in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. In particular, solution calorimetry data of apatite compositions along the F-Cl join exhibit substantial excess enthalpies of mixing. In the present study, we conducted apatite-melt partitioning experiments in evacuated, sealed silica-glass tubes at approximately 1 bar and 950-1050 degrees Centigrade on a synthetic Martian basalt composition equivalent to the basaltic shergottite Queen Alexandria Range (QUE) 94201. These experiments were conducted dry, at low pressure, to assess the effects of temperature and apatite composition on the partitioning behavior of F and Cl between apatite and basaltic melt along the F-Cl apatite binary join, where there is non-ideal mixing of F and Cl in apatite

Using Simulated Micrometeoroid Impacts to Understand the Progressive Space Weathering of the Surface of Mercury

The surfaces of airless bodies such as Mercury are continually modified by space weathering, which is driven by micrometeoroid impacts and solar wind irradiation. Space weathering alters the chemical composition, microstructure, and spectral properties of surface regolith. In lunar and ordinarychondritic style space weathering, these processes affect the reflectance properties by darkening (lowering of reflectance), reddening (increasing reflectance with increasing wavelength), and attenuation of characteristic absorption features. These optical changes are driven by the production of nanophase Febearing particles (npFe). While our understanding of these alteration processes has largely been based on data from the Moon and near-Earth S-type asteroids, the space weathering environment at Mercury is much more extreme. The surface of Mercury experiences a more intense solar wind flux and higher velocity micrometeoroid impacts than its planetary counterparts at 1 AU. Additionally, the composition of Mercurys surface varies significantly from that of the Moon. Most notably, a very low albedo unit has been identified on Mercurys surface, known as the low reflectance material (LRM). This unit is enriched with up to 4 wt.% carbon, likely in the form of graphite, over the local mean. In addition, the surface concentration of Fe across Mercurys surface is low (<2 wt.%) compared to the Moon. Our understanding of how these low-Fe and carbon phases are altered as a result of space weathering processes is limited. Since Fe plays a critical role in the development of space weathering features on other airless surfaces (e.g., npFe), its limited availability on Mercury may strongly affect the space weathering features in surface materials. In order to understand how space weathering affects the chemical, microstructural, and optical properties of the surface of Mercury, we can simulate these processes in the laboratory [7]. Here we used pulsed laser irradiation to simulate the short duration, high temperature events associated with micrometeoroid impacts. We used forsteritic olivine, likely present on the Mercurian surface, with varying FeO contents, each mixed with graphite, in our experiments. We then performed reflectance spectroscopy and electron microscopy to investigate the spectral, chemical, and microstructural changes in these samples

Meteorite Dust and Health - A Novel Approach for Determining Bulk Compositions for Toxicological Assessments of Precious Materials

With the resurgence of human curiosity to explore planetary bodies beyond our own, comes the possibility of health risks associated with the materials covering the surface of these planetary bodies. In order to mitigate these health risks and prepare ourselves for the eventuality of sending humans to other planetary bodies, toxicological evaluations of extraterrestrial materials is imperative (Harrington et al. 2017). Given our close proximity, as well as our increased datasets from various missions (e.g., Apollo, Mars Exploration Rovers, Dawn, etc), the three most likely candidates for initial human surface exploration are the Moon, Mars, and asteroid 4Vesta. Seven samples, including lunar mare basalt NWA 4734, lunar regolith breccia NWA 7611, martian basalt Tissint, martian regolith breccia NWA 7034, a vestian basalt Berthoud, a vestian regolith breccia NWA 2060, and a terrestrial mid-ocean ridge basalt, were examined for bulk chemistry, mineralogy, geochemical reactivity, and inflammatory potential. In this study, we have taken alliquots from these samples, both the fresh samples and those that underwent iron leaching (Tissint, NWA 7034, NWA 4734, MORB), and performed low pressure, high temperature melting experiments to determine the bulk composition of the materials that were previously examined

Making Mercury's Core with Light Elements

Recent results obtained from the MErcury Surface, Space ENvironment, GEochemistry, and Ranging spacecraft showed the surface of Mercury has low FeO abundances (less than 2 wt%) and high S abundances (approximately 4 wt%), suggesting the oxygen fugacity of Mercury's surface materials is somewhere between 3 to 7 log10 units below the IW buffer. The highly reducing nature of Mercury has resulted in a relatively thin mantle and a large core that has the potential to exhibit an exotic composition in comparison to the other terrestrial planets. This exotic composition may extend to include light elements (e.g., Si, C, S). Furthermore, has argued for a possible primary floatation crust on Mercury composed of graphite, which may require a core that is C-saturated. In order to investigate mercurian core compositions, we conducted piston cylinder experiments at 1 GPa, from 1300 C to 1700 C, using a range of starting compositions consisting of various Si-Fe metal mixtures (Si5Fe95, Si10Fe90, Si22Fe78, and Si35Fe65). All metals were loaded into graphite capsules used to ensure C-saturation during the duration of each experimental run. Our experiments show that Fe-Si metallic alloys exclude carbon relative to more Fe-rich metal. This exclusion of carbon commences within the range of 5 to 10 wt% Si. These results indicate that if Mercury has a Si-rich core (having more than approximately 5 wt% silicon), it would have saturated in carbon at low C abundances allowing for the possible formation of a graphite floatation crust as suggested by. These results have important implications for the thermal and magmatic evolution of Mercury

Experimental Study into the Partitioning Behavior of Fluorine, Chlorine, Hydroxyl, and Sulfur (S2-) Between Apatite and a Synthetic Kreep Basalt Melt

The mineral apatite (Ca5 (PO4)3(F, Cl, OH)) is known for its ability to constrain the petrogenesis of the rock in which it is hosted and for its ubiquity throughout the Solar System, as it is found in lunar, martian, and terrestrial rocks alike (McCubbin et. al, 2015). The abundance of volatile elements, and for this particular study, the elevated abundance of sulfur (S2-) in high-Al basalt samples bearing apatite, could provide more insight for inquiries posed about the behavior of volatiles in lunar and martian magmatic systems (Boyce et. al, 2010). Oxygen fugacity will be an important parameter for these experiments, as the Moon, Mars, and Earth have different redox states (Herd, 2008). The objective of this experimental endeavor is to determine apatite-melt partition coefficients for the volatile elements (F-, Cl-, OH-, S2-) that make up the X-site (i.e., the typically monovalent anion site) in the mineral apatite in a lunar melt composition under lunar oxygen fugacity conditions approx.1-2 log units below the iron-wstite buffer). All experiments will be conducted at NASA, Johnson Space Center in the High Pressure Experimental Petrology Laboratory. In order to conduct apatite-melt partition experiments with oxygen fugacity as an additional parameter, we will create a synthetic mix of the lunar KREEP basalt 15386, a sample retrieved during Apollo 15 that is believed to represent an indigenous volcanic melt derived from the lunar interior (Rhodes, J.M et. al, 2006). Other geochemically significant elements including C, Co, Ni, Mo, and rare earth elements will be included in the mix at trace abundances in order to assess their partitioning behavior without effecting the overall behavior of the system. The synthetic mix will then be loaded into a piston cylinder, an apparatus used to simulate high-pressure/high-temperature conditions of planetary interiors, and exposed to 0.5 GPa of pressure, the pressure observed in the upper mantle of the Moon, and heated to the melting temperature of the materials. To make sure crystals grow large enough for the necessary analyses, the sample will be kept at the crystallization temperature for 8 hours. This extended run time should also allow the sample to achieve a steady state which is necessary to accurately assess the partitioning of these elements between apatite and melt. The results from this experimental study will allow us to determine the fate of F-, Cl-, OH-, and S2- during the magmatic evolution of the Moon

Assessing the Behavior of Typically Lithophile Elements Under Highly Reducing Conditions Relevant to the Planet Mercury

With the data returned from the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (lvtESSENGER) mission, there are now numerous constraints on the physical and chemical properties of Mercury, including its surface composition. The high S and low FeO contents observed from MESSENGER suggest a low oxygen fugacity of the present materials on the planet's surface. Most of our understanding of elemental partitioning behavior comes from observations made on terrestrial rocks, but Mercury's oxygen fugacity is far outside the conditions of those samples, estimated at approximately 3-7 log units below the Iron-Wustite (lW) oxygen buffer, several orders of magnitude more reducing than other terrestrial bodies we have data from. With limited oxygen available, lithophile elements may instead exhibit chalcophile, halophile, or siderophile behaviors. Furthermore, very few natural samples of rocks that formed under reducing conditions (e.g., enstatite chondrites, achondrites, aubrites) are available in our collections for examination of this change in geochemical affinity. Our goal is to determine the elemental partitioning behavior of typically lithophile elements at lower oxygen fugacity as a function of temperature and pressure. Experiments were conducted at I GPa in a 13 mm QUICKpress piston cylinder and at 4 GPa in an 880-ton multi-anvil press, at temperatures up to 1850 C. The composition of starting materials for the experiments were designed so the final run products contained metal, silicate melt, and sulfide melt phases. Oxygen fugacity was controlled in the experiments by adding silicon metal to the samples, in order to utilize the Si-Si02 buffer, which is approx. 5 log units more reducing than the IW buffer at our temperatures of interest. The target silicate melt composition was diopside (CaMgSi206) because measured surface compositions indicate partial melting of a pyroxene-rich mantle. The results of our experiments will aid in our understanding of the fate of elements during the differentiation and thermal evolution of Mercury and other highly reducing planetary bodies