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Vander Kaaden, K. E.

Publications and source records attributed to Vander Kaaden, K. E..

At least 19 records

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 µm) 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 µm are ~0.95 [5-8]. This can be tested by measureing reflectance, because Kirchoff’s 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 e’s 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 25°C [9,10]. However, these measurements have been updated [7,8] and are consistent with the results here (see below and Fig. 3).

Treiman, A. H.↗

Geochemical Advances in Mercury Science Facilitated by a Landed Mission

The data from the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft have revealed several surprising characteristics about the surface of Mercury, leading to its classification as a geochemical endmember among the terrestrial planets. Some of these features include elevated abundances of up to 3 wt% S, C enrichment as high as 4 wt% over the local mean in low reflectance materials (LRM), Na up to 5 wt% at high northern latitudes, and Fe abundances typically lower than 2 wt% [e.g., 1–4]. The S and Fe concentrations have been used to infer that Mercury’s igneous history evolved under highly reduced oxygen fugacity conditions between 2.6 and 7.3 log10 units below the iron-wüstite buffer [e.g., 5], which is more reducing than any other terrestrial planet in the solar system [e.g., 6]. This highly reduced nature has important consequences for the differentiation and thermal/magmatic evolution of Mercury. While the immense amount of data collected by MESSENGER revealed Mercury as a geochemical endmember, this new knowledge gained raised additional questions that necessitate continued exploration of the planet. Fortunately, BepiColombo launched in October of 2018, and this joint ESA/JAXA dual-orbiter spacecraft is the most ambitious effort yet attempted to explore Mercury [e.g., 7]. Looking beyond BepiColombo, there are major aspects of Mercury’s geochemical character and evolution for which significant knowledge gaps can be dramatically improved with data acquired from the planet’s surface via in situ landed science.

Vander Kaaden, K. E.↗

Stability of Actinolite on Venus

Venus currently has a hostile surface environment with temperatures of ~460 ºC, pres-sures near 92 bars, and an atmosphere composed of super critical CO2 hosting a myriad of other potentially reactive gases (e.g., SO2, HCl, HF). However, it has been proposed that its surface may not have always been so harsh. Models suggest there may have been billions of years of clement conditions allowing an Earth-like environment with liquid water oceans. If such conditions existed, it is possible Venus formed a similar array of hydrous or aqueous minerals as seen on other planets with liquid surface water (e.g., Mars, Earth). Based on thermodynamic modeling, many of these phases would not be stable under the current atmospheric conditions on Venus, dehydrating due to the high temperatures and low concentration of H2O in the atmosphere. However, the rate of decomposition of these phases may allow them to remain present on the surface over geologic time. For example, experiments on the reaction rate of tremolite (Ca2Mg5Si8O22(OH)2) show a 50% decomposition time of 2.7 Gyr for micrometer sized grains in unreactive atmospheres (i.e., without SO2) at 740 K, and a 50% decomposition time of 70 Gyr for crystals several millimeters to centimeters in size. If hydrous minerals can remain on the surface of Venus over geologic time, it has implications for our detection of evidence of these past environments, and also for the overall water budget of the planet. If after surficial dehydration the planet was able to still store water in its crust, possible processes such as subduction or metamorphism could still have operated using stored water long after liquid surface water evaporated. Several previous studies have focused on experimental investigations of mineral stability on Venus. In particular, the works of studied the decomposition rate of tremolite under conditions relevant to Venus. As their focus was on decomposition of the mineral due to lack of water in the atmosphere, their experiments were undertaken using only CO2 or N2 gas at atmospheric pressure. Re-cent experiments have examined reactivity of other minerals with the Venusian atmosphere using more complex gas compositions at similar pressures to those seen on Venus. These studies show reaction of silicate minerals with atmospheric components on relatively short timescales (i.e., on the order of days). The reported reactions of silicate materials in both studies produced iron oxides, Ca sulfates, and Na sulfates. These ions are present in many amphiboles, and Ca was proposed by Johnson and Fegley to potentially have an important role in the decomposition mechanism for tremolite, with the Ca-O bond being the first to break during decomposition. The potential involvement of Ca in both processes raises the question of whether or not the reaction to form a secondary mineral phase will influence the rate of amphibole break-down (e.g., discussion in for tremolite). Additionally, reaction of Ca with atmospheric gases may result in a different secondary mineral assemblage than simple amphibole decomposition, which will need to be recognized when searching for evidence of past hydrated minerals on the Venusian surface. In order to understand the effect of this reaction on the overall preservation potential of amphibole on the surface of Venus, we are conducting experiments in both reactive and nonreactive atmospheres using the mineral actinolite (Ca2(Mg,Fe)5Si8O22(OH)2), an amphibole with similar crystal structure to tremolite that contains both Ca and Fe.

Santos, A. R.↗

Cardiopulmonary Inflammatory Response to Meteorite Dust Exposures - Implications for Human Health on Earth and Beyond

This year marks the 50th anniversary of Apollo 11, the first time humans set foot on the Moon. The Apollo missions not only help answer questions related to our solar system, they also highlight many hazards associated with human space travel. One major concern is the effect of extraterrestrial dust on astronaut health. In an effort to expand upon previous work indicating lunar dust is respirable and reactive, the authors initiated an extensive study evaluating the role of a particulate’s innate geochemical features (e.g., bulk chemistry, internal composition, morphology, size, and reactivity) in generating adverse toxicological responses in vitro and in vivo. To allow for a broader planetary and geochemical assessment, seven samples were evaluated: six meteorites from either the Moon, Mars, or Asteroid 4 Vesta and a terrestrial basalt analogue. Even with the relatively small geochemical differences (all samples basaltic in nature), significant difference in cardiopulmonary inflammatory markers developed in both single exposure and multiple exposure studies. More specifically: 1) the single exposure studies reveal relationships between toxicity and a meteorite sample’s origin, its pre-ejected state (weathered versus un-weathered), and geochemical features (e.g. bulk iron content) and 2) multiple exposure studies reveal a correlation with particle derived reactive oxygen species (ROS) formation and neutrophil infiltration. Extended human exploration will further increase the probability of inadvertent and repeated exposures to extraterrestrial dusts. This comprehensive dataset allows for not only the toxicological evaluation of extraterrestrial materials but also clarifies important correlations between geochemistry and health. The utilization of an array of extraterrestrial samples from Moon, Mars, and asteroid 4Vesta will enable the development of a geochemical based toxicological hazard model that can be used for: 1) mission planning, 2) rapid risk assessment in cases of unexpected exposures, and 3) evaluation of the efficacy of various in situ techniques in gauging surface dust toxicity. Furthermore, by better understanding the importance of geochemical features on exposure related health outcomes in space, it is possible to better understand of the deleterious nature of dust exposure on Earth.

Harrington, A. D.↗

Near-Infrared Reflectance Spectroscopy of Venus-Analog Rocks at Venus Surface Temperatures

Venus’ surface can be viewed in emission through the relatively opaque atmosphere via a few spectral ‘windows’ in the near-infrared (NIR, most near 1 μm). Venus’ surface appears to show emissivities that correlate with surface geology, and these emissivity variations are interpreted as differences in surface rock type (mafic vs. silicic) and/or extent of weathering (Fe(2+) silicates vs. Fe(3+)-oxide-coated). To understand and quantify the observed variations in NIR emissivity, laboratories are measuring high-T NIR emissivity directly. For example, the measured emissivities of basalts in the wavelength range 0.85 – 1.2 μm are ~0.9. This value can be tested by measurement of reflectance, because Kirchoff’s Law holds that emissivity (e) = 1 – reflectance (r). The r of basalt in the NIR is ~0.1 so its e should be ~0.9. However, high-T NIR e’s of silicic igneous rocks (granitic, rhyolite) are reported to be 0.8-0.9, which is inconsistent with r values of 0.3-0.7 of such rocks at room-T. For both datasets to be correct, the r values of silicic igneous rock would have to decrease precipitously between room and Venus surface temperatures. This seems unlikely.

Treiman, A. H.↗

Understanding the Space Weathering of Mercury via Simulation of Micrometeorite Impacts

Space weathering alters the surfaces of airless planetary bodies via irradiation from the solar wind and micrometeorite impacts. These processes modify the microstructure, chemical composition, and spectral properties of surface materials, typically resulting in the reddening (increasing reflectance with increasing wavelength), darkening (reducing albedo), and attenuation of characteristic absorption features in reflectance spectra. In lunar samples, these changes in optical properties are driven by the production of reduced nanophase Fe particles (npFe). Our understanding of space weathering has largely been based on data from the Moon and, more recently, near-Earth S-type asteroids. However, the environment at Mercury is significantly different, with the surface experiencing intense solar wind irradiation and higher velocity micrometeorite impacts. Additionally, the composition of Mercury’s surface varies significantly from that of the Moon, including a component with very low albedo known as low reflectance material (LRM) which is enriched with up to 4 wt.% carbon over the local mean. Our understanding of how carbon phases, including graphite, are altered as a result of these processes is limited.

McGlaun, M. L.↗

Pulmonary Inflammatory Responses to Acute Meteorite Dust Exposures - Implications for Human Space Exploration

New initiatives to begin Lunar and Martian human surface operations within the next few decades are illustrative of the resurgence of interest in human space exploration. However, as with all exploration, there are risks. The previous manned missions to the Moon highlight a major hazard for future human exploration of the Moon and beyond: surface dust. Not only did the dust cause mechanical and structural integrity issues with the suits, the dust 'storm' generated upon reentrance into the crew cabin caused "lunar hay fever" and "almost blindness.". It was further reported that the allergic response to the dust worsened with each exposure. Due to the prevalence of these high exposures, the Human Research Roadmap developed by NASA identifies the Risk of Adverse Health and Performance Effects of Celestial Dust Exposure as an area of concern.

Harrington, A. D.↗

Experimental Investigation of Chromium Behavior During Mercury's Differentiation

Mercury is the most reduced terrestrial planet with the largest core/mantle size ratio and highest sulfur concentration on the surface. The MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft data allowed mapping of Mercury's surface elemental composition. Recent chromium mapping suggests Mercury's surface has on average 800 parts per million Cr with the highest values in the High Magnesium Region. These new data can give clues about Mercury's internal structure and the redox conditions under which it differentiated. In the present study, we present experimental data on the distribution of Cr among metal, silicate and sulfide liquids. We then combine them with data from previous studies and a model of planetary differentiation to discuss Mercury's bulk composition and its oxidation state.

Boujibar, A.↗

Heterogeneous Distribution of Chromium on Mercury

Measurements made with geochemical instruments on the MESSENGER spacecraft revealed that Mercury's crust is surprisingly rich in volatile elements, including S, Na, K, Cl, and C, and that it is enriched in Mg and depleted in Al, Ca, and Fe, relative to other terrestrial planets. Geochemical maps also indicated the presence of a number of distinct geochemical terranes. The MESSENGER X-ray Spectrometer (XRS) detected X-ray fluorescence, induced by incident solar X-rays, from the top approx. 10s of micrometers of Mercury's surface. Like Fe, Cr was only detectable by XRS during large solar flares. However, accurate Cr measurements are more susceptible to systematic errors than other elements measured by the XRS. Therefore, to date, Cr data have been published for only 11 XRS measurements, but we have recently derived a map of Cr/Si across Mercury's surface. This map is based on data acquired through the complete MESSENGER mission and reveals clear spatial heterogeneity in Cr.

Nittler, L. R.↗

Aubrite and Enstatite Chondrite Impact Melt Meteorites: Analogs to Mercury?

New data obtained during the MESSENGER mission has allowed us to better contrain the composition and mineralogy of the mercurian surface. One unique feature of Mercury is its extremely low oxygen fugacity (ƒO2) (Iron Wustite (IW) -7.3 to IW-2.6). At such extreme conditions, elements that exhibit lithophile behavior on Earth can exhibit chalcophile or siderophile behavior, leading to the formation of exotic sulfides and metals. As no samples have been returned from Mercury, it is critical to study meteorite analogs to better under-stand the formation conditions of the minerals present at the mercurian surface, as well as mercurian magmatic processes. Given the low fO2 on Mercury, we have selected to investigate potential meteoritic analogs for Mercury among the most reduced meteorite types, including the aubrites and enstatite chondrite impact melts. The aubrites are differentiated meteorites that show varying degrees of brecciation, have a similar ƒO2 to the mercurian surface and interior, and contain exotic sulfides that have been inferred to be present on the mercurian surface. The enstatite chondrite impact melts are from undifferentiated parent bodies, have a similar ƒO2 to the mercurian surface and interior, and contain exotic sulfides that have been inferred to be present on the mercurian surface. In this study, we present a comprehensive analysis of a representative suite of aubrites and enstatite chondrite impact melts and assess their relevance to under-standing magmatic processes on Mercury.

Wilbur, Z. E.↗

Can Silicon-Smelting Contribute to the Low O/Si Ratio on the Surface of Mercury?

The MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft collected data that provided important insights into the structure, chemical makeup, and compositional diversity of Mercury. Among the many discoveries about Mercury made by MESSENGER, several surprising compositional characteristics of the surface were observed. These discoveries include elevated sulfur abundances (up to 4 wt.%), elevated abundances of graphitic carbon (0-4.1 wt.% across the surface with an additional 1-3 wt.% graphite above the global average in low reflectance materials), low iron abundances (less than 2 wt.%), and low oxygen abundances (O/Si weight ratio of 1.20+/-0.1). These exotic characteristics likely have important implications for the thermochemical evolution of Mercury and point to a planet that formed under highly reducing conditions. In the present study, we focus specifically on the low O/Si ratio of Mercury, which is anomalous compared to all other planetary materials. A recent study that considered the geochemical implications of the low O/Si ratio reported that 12-20% of the surface materials on Mercury are composed of Si-rich, Si-Fe alloys. They further postulated that the origin of the metal is best explained by a combination of space weathering and graphite-induced smelting that was facilitated by interaction of graphite with boninitic and komatiitic parental liquids. The goal of the present study is to assess the plausibility of smelting on Mercury through experiments run at the conditions that McCubbin et al. indicated would be favorable for Si-smelting.

McCubbin, F. M.↗

Experimental Study into the Stability of Whitlockite and Hydroxylapatite in Basaltic Magmas

Apatite (Ca5(PO4)3(F,Cl,OH)), merrillite (Ca18Na2Mg2(PO4)14), and whitlockite (Ca9(Mg,Fe(2+))(PO4)6[PO3(OH)]) are the primary phosphate minerals found in most planetary materials including rocks from Earth, Moon, Mars, and asteroids. For many years, the terms merrillite and whitlockite have been used interchangeably in the meteorite literature. Much of the confusion regarding the relationship between terrestrial and extraterrestrial 'whitlockite' is based on the presence or absence of hydrogen in the mineral structure. Whitlockite has approximately 8500 ppm H2O, and the term 'merrillite' has been adopted to identify the hydrogen-free form of whitlockite. The atomic structures of merrillite and whitlockite were examined in detail by Hughes et al.. On Earth, whitlockite has been found in rocks from evolved pegmatitic systems and in some mantle rocks. Furthermore, terrestrial whitlockite has been shown to have some merrillite component. For the meteoritic and lunar materials that have been investigated, merrillite appears to be far more common than whitlockite, and it has been proposed that the whitlockite component is unique to terrestrial samples. There are some reports of 'whitlockite' in the meteorite literature; however, these may represent misidentifications of merrillite because there have been no reports of extraterrestrial whitlockite that have been verified through crystal structural studies or analyzed for their H contents. Hughes et al. reported the atomic arrangement of lunar merrillite and demonstrated that the phase is similar to meteoritic merrillite and, predictably, devoid of hydrogen. In a follow-up study, Hughes et al. reported the atomic arrangements of two natural samples of whitlockite, one synthetic whitlockite, and samples of synthetic whitlockite that were heated at 500 C or 1050 C for 24 h. The crystal chemistry and crystal structures of the phases were compared, and it was discovered that the latter treatment resulted in the dehydrogenation of whitlockite to form merrillite.

McCubbin, F. M.↗

Pulmonary Inflammatory Responses to Acute Meteorite Dust Exposures - Implications for Human Space Exploration

New initiatives to send humans to Mars within the next few decades are illustrative of the resurgence of interest in space travel. However, as with all exploration, there are risks. The Human Research Roadmap developed by NASA identifies the Risk of Adverse Health and Performance Effects of Celestial Dust Exposure as an area of concern. Extended human exploration will further increase the probability of inadvertent and repeated exposures to celestial dusts.

Harrington, A. D.↗

Exploring the Utilization of Low-Pressure, Piston-Cylinder Experiments to Determine the Bulk Compositions of Finite, Precious Materials

Determining the bulk composition of precious materials with a finite mass (e.g., meteorite samples) is extremely important in the fields of Earth and Planetary Science. From meteorite studies we are able to place constraints on large scale planetary processes like global differentiation and subsequent volcanism, as well as smaller scale processes like crystallization in a magma chamber or sedimentary compaction at the surface. However, with meteorite samples in particular, far too often we are limited by how precious the sample is as well as its limited mass. In this study, we have utilized aliquots of samples previously studied for toxicological hazards, including both the fresh samples (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 (MORB)), and those that underwent iron leaching (Tissint, NWA 7034, NWA 4734, MORB). With these small masses of material, we performed low pressure (approx. 0.75 GPa), high temperature (greater than 1600 degrees Celsius) melting experiments. Each sample was analyzed using a JEOL 8530F electron microprobe to determine the bulk composition of the materials that were previously examined. When available, the results of our microprobe data were compared with bulk rock compositions in the literature. The results of this study show that with this technique, only approx. 50 mg of sample is required to accurately determine the bulk composition of the materials of interest.

Vander Kaaden, K. E.↗

Experimental Study into the Stability of Whitlockite in Basaltic Magmas

Apatite Ca5(PO4)3(F,Cl,OH), merrillite Ca18Na2Mg2(PO4)14, and whitlockite Ca9(Mg,Fe2+)(PO4)6[PO3(OH)] are the primary phosphate minerals found in most planetary materials including rocks from Earth, Moon, Mars, and asteroids [1-2]. For many years, the terms merrillite and whitlockite have been used interchangeably in the meteorite literature. Much of the confusion regarding the relationship between terrestrial and extraterrestrial "whitlockite" is based on the presence or absence of hydrogen in the mineral structure. Whitlockite has approximately 8500 ppm H2O, and the term "merrillite" has been adopted to identify the hydrogen-free form of whitlockite [2]. The atomic structures of merrillite and whitlockite were examined in detail by Hughes et al. [3-4]. On Earth, whitlockite has been found in rocks from evolved pegmatitic systems [2-4] and in some mantle rocks [e.g., 5]. Furthermore, terrestrial whitlockite has been shown to have some merrillite component [4]. For the meteoritic and lunar materials that have been investigated, merrillite appears to be far more common than whitlockite, and it has been proposed that the whitlockite component is unique to terrestrial samples [4]. There are some reports of "whitlockite" in the meteorite literature; however, these likely represent misidentifications of merrillite because there have been no reports of extraterrestrial whitlockite that have been verified through crystal structural studies or analyzed for their H contents. Hughes et al. [3] reported the atomic arrangement of lunar merrillite and demonstrated that the phase is similar to meteoritic merrillite and, predictably, devoid of hydrogen. In a follow-up study, Hughes et al. [4] reported the atomic arrangements of two natural samples of whitlockite, one synthetic whitlockite, and samples of synthetic whitlockite that were heated at 500degC and 1050degC for 24 h. The crystal chemistry and crystal structures of the phases were compared, and it was discovered that the latter treatment resulted in the dehydrogenation of whitlockite to form merrillite. The presence of merrillite vs. whitlockite was widely thought to serve as an indication that magmas were anhydrous [e.g., 6-7]. However, McCubbin et al., [8] determined that merrillite in the martian meteorite Shergotty had no discernible whitlockite component despite its coexistence with OH-rich apatite. Consequently, McCubbin et al., (2014) speculated that the absence of a whitlockite component in Shergotty merrillite and other planetary merrillites may be a consequence of the limited thermal stability of H in whitlockite (stable only at T less than1050degC), which would prohibit merrillite-whitlockite solid-solution at high temperatures. In the present study, we have aimed to test this hypothesis experimentally by examining the stability of whitlockite in basaltic magmas at 1.2 GPa and a temperature range of -1000- 1300degC.

McCubbin, F. M.↗

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.

Vander Kaaden, K. E.↗

Endogenous Lunar Volatiles

The chapter will begin with an introduction that defines magmatic volatiles (e.g., H, F, Cl, S) versus geochemical volatiles (e.g., K, Rb, Zn). We will discuss our approach of understanding both types of volatiles in lunar samples and lay the ground work for how we will determine the overall volatile budget of the Moon. We will then discuss the importance of endogenous volatiles in shaping the "Newer Views of the Moon", specifically how endogenous volatiles feed forward into processes such as the origin of the Moon, magmatic differentiation, volcanism, and secondary processes during surface and crustal interactions. After the introduction, we will include a re-view/synthesis on the current state of 1) apatite compositions (volatile abundances and isotopic compositions); 2) nominally anhydrous mineral phases (moderately to highly volatile); 3) volatile (moderately to highly volatile) abundances in and isotopic compositions of lunar pyroclastic glass beads; 4) volatile (moderately to highly volatile) abundances in and isotopic compositions of lunar basalts; 5) volatile (moderately to highly volatile) abundances in and isotopic compositions of melt inclusions; and finally 6) experimental constraints on mineral-melt partitioning of moderately to highly volatile elements under lunar conditions. We anticipate that each section will summarize results since 2007 and focus on new results published since the 2015 Am Min review paper on lunar volatiles [9]. The next section will discuss how to use sample abundances of volatiles to understand the source region and potential caveats in estimating source abundances of volatiles. The following section will include our best estimates of volatile abundances and isotopic compositions (where permitted by available data) for each volatile element of interest in a number of important lunar reservoirs, including the crust, mantle, KREEP, and bulk Moon. The final section of the chapter will focus upon future work, outstanding questions, and any in-sights on the types of samples or experimental studies that will be needed to answer these questions.

McCubbin, F. M.↗

Partitioning of F and Cl Between Apatite and a Synthetic Shergottite Liquid (QUE 94201) at 4 Gpa from 1300 TO 1500 C

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 (Xsite), 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 accurately determine the abundances of volatiles in coexisting silicate melt or fluids, thermodynamic models for the apatite solid solution and for the apatite components in multicomponent 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 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, and McCubbin et al. reported substantial deviations in the Cl-F exchange Kd along the F-Cl apatite join that could be explained by the preferential incorporation of F into apatite. In the present study, we assess the effect of apatite crystal chemistry on F-Cl exchange equilibria between apatite and melt at 4 GPa over the temperature range of 1300-1500 C. The goal of these experiments is to assess the variation in the Ap-melt Cl-F exchange Kd over a broad range of F:Cl ratios in apatite. The results of these experiments could be used to understand at what composition apatite shifts from a hexagonal unit cell with space group P63/m to a unit cell with monoclinic symmetry within space group P21/b. We anticipate that this transition occurs at >70% chlorapatite based on solution calorimetry data.

McCubbin, F. M.↗