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NASA NTRS2020

The Chlorine-Isotopic Composition of Lunar KREEP From Magnesian-Suite Troctolite 76535

We conducted in-situ Cl isotopic measurements of apatite within intercumulus regions and within a holocrystalline olivine-hosted melt inclusion in magnesian-suite troctolite 76535 from Apollo 17. These data were collected to place constraints on the Cl-isotopic composition of the last liquid to crystallize from the lunar magma ocean (i.e., urKREEP, named after its enrichments in incompatible lithophile trace elements like potassium, rare earth elements, and phosphorus). The apatite in the olivine-hosted melt inclusion and within the intercumulus regions of the sample yielded Cl-isotopic compositions of 28.3 ± 0.9 ‰ (2σ) and 30.3 ± 1.1 ‰ (2σ), respectively. The concordance of these values from both textural regimes we analyzed indicates that the Cl-isotopic composition of apatites in 76535 likely represents the Cl-isotopic composition of the KREEP-rich magnesian-suite magmas. Based on the age of 76535, these results imply that the KREEP reservoir attained a Cl-isotopic composition of 28–30 ‰ by at least 4.31 Ga, consistent with the onset of Cl-isotopic fractionation at the time of lunar magma ocean crystallization or shortly thereafter. Moreover, lunar samples that yield Cl-isotopic compositions higher than the value for KREEP are likely affected by secondary processes such as impacts and/or magmatic degassing. The presence of KREEP-rich olivine-hosted melt inclusions within one of the most pristine and ancient KREEP-rich rocks from the Moon provides a new opportunity to characterize the geochemistry of KREEP. In particular, a broader analysis of stable isotopic compositions of highly and moderately volatile elements could provide an unprecedented advancement in our characterization of the geochemical composition of the KREEP reservoir and of volatile-depletion processes during magma ocean crystallization, more broadly.

Francis M. McCubbin↗
NASA NTRS2021

Investigation of several proxies to estimate sulfuric acid concentration in volcanic plume conditions

Sulfuric acid (H2SO4) is commonly accepted as a key precursor for atmospheric new particle formation (NPF). However, direct measurements of [H2SO4] remain challenging, thus preventing the determination of this important quantity, and, consequently, a complete understanding of its contribution to the NPF process. Several proxies have been developed to bridge the gaps, but their ability to predict [H2SO4] in very specific conditions such as those encountered in volcanic plumes (including in particular high sulphur dioxide mixing ratios) has not been evaluated so far. In this context, the main objective of the present study was to develop new proxies for daytime [H2SO4] in volcanic plume conditions and compare their performance to that of the proxies available in the literature. In specific, the data collected at Maïdo during the OCTAVE 2018 campaign, in the volcanic eruption plume of the Piton de la Fournaise, were first used to derive seven proxies based on the knowledge of sulphur dioxide (SO2) mixing ratio, global radiation, condensation sink (CS) and relative humidity (RH). In three of the seven proxies (F1–F3), all variables were given equal weight in the prediction of [H2SO4], while adjusted powers were allowed for the different variables in the other four proxies (A1–A4). Proxies A1–A4 were overall found to perform better compared to F1–F3, with, in specific, improved predictive ability for [H2SO4] > 2 × 108 per cu.cm. The CS was observed to play an important role in regulating [H2SO4], while, in contrast, the inclusion of RH did not improve the predictions. A last expression accounting for an additional sink term related to cluster formation, S1, was also tested and showed a very good predictive ability over the whole range of measured [H2SO4]. The newly developed proxies were in a second step further evaluated using airborne measurements performed in the passive degassing plume of Etna during the STRAP 2016 campaign. Increased correlations between observed and predicted [H2SO4] were obtained when the dependence of predicted [H2SO4] over CS was the lowest, and when the dependence over [SO2] was concurrently the highest. The best predictions were finally retrieved by the simple formulation of F2 (in which [SO2] and radiation alone were assumed to explain the variations of [H2SO4] with equal contributions), with a pre factor adapted to the STRAP data. All in all, our results illustrate the fairly good capacity of the proxy available in the literature to describe [H2SO4] in volcanic plume conditions, but highlight at the same time the benefit of the newly developed proxies for the prediction of the highest concentrations ([H2SO4] > 2–3 × 108 per cu.cm). Also, the contrasting behaviours of the new proxies in the two investigated datasets indicate that in volcanic plumes like in other environments, the relevance of a proxy can be affected by changes in environmental conditions, and that location specific coefficients do logically improve the predictions.

new particle formation↗
NASA NTRS2021

VESIcal Part I: An open-source thermodynamic model engine for mixed volatile (H2O-CO2) solubility in silicate melts

Thermodynamics has been fundamental to the interpretation of geologic data and modeling of geologic systems for decades. However, more recent advancements in computational capabilities and a marked increase in researchers’ accessibility to computing tools has outpaced the functionality and extensibility of currently available modeling tools. Here we present VESIcal (Volatile Equilibria and Saturation Identification calculator): the first comprehensive modeling tool for H 2 O, CO 2 , and mixed (H 2 O-CO 2 ) solubility in silicate melts that: a) allows users access to seven commonly used models, plus easy inter-comparison between models; b) provides universal functionality for all models (e.g., functions for calculating saturation pressures, degassing paths, etc.); c) can process large datasets (1,000’s of samples) automatically; d) can output computed data into an excel spreadsheet for simple post-modeling analysis; e) integrates advanced plotting capabilities directly within the tool; and f) provides all of these within the framework of a python library, making the tool extensible by the user and allowing any of the model functions to be incorporated into any other code capable of calling python. The tool is presented within this manuscript, which is a Jupyter notebook containing worked examples accessible to python users with a range of skill levels. The basic functions of VESIcal can also be access via a web app (https://vesical.anvil.app). The VESIcal python library is open-source and available for download at https://github.com/kaylai/VESIcal.

K. Iacovino↗
NASA NTRS2022

VESIcal: A Critical Approach to Volatile Solubility Modelling Using the Open-Source Engine Vesical

Accurate models of H(2)O and CO(2) solubility in silicate melts are vital for understanding volcanic plumbing systems. These models are used to estimate the depths of magma storage regions from melt inclusion volatile contents, investigate the role of volatile exsolution as a driver of volcanic eruptions, and track the degassing path followed by a magma ascending to the surface. However, despite the large increase in the number of experimental constraints over the last two decades, many recent studies still utilize an earlier generation of models which were calibrated on experimental datasets with restricted compositional ranges. This may be because many of the available tools for more recent models require large numbers of input parameters to be hand-typed (e.g., temperature, concentrations of H(2)O, CO(2), and 8–14 oxides), making them difficult to implement on large datasets. Here, we use a new open-source Python3 tool, VESIcal, to critically evaluate the behaviors and sensitivities of different solubility models for a range of melt compositions. Using literature datasets of andesitic-dacitic experimental products and melt inclusions as case studies, we illustrate the importance of evaluating the calibration dataset of each model. Finally, we highlight the limitations of particular data presentation methods, such as isobar diagrams, and provide suggestions for alternatives, and best practices regarding the presentation and archiving of data. This review will aid the selection of the most applicable solubility model for different melt compositions, and identifies areas where additional experimental constraints on volatile solubility are required.

magma↗
NASA NTRS2022

Scientific Value of Including an Atmospheric Sample as Part of Mars Sample Return (MSR)

The Perseverance rover is meant to collect samples of the martian surface for eventual return to Earth. The headspace gas present over the solid samples within the sample tubes will be of significant scientific interest for what it reveals about the interactions of the solid samples with the trapped atmosphere and for what it will reveal about the martian atmosphere itself. However, establishing the composition of the martian atmosphere will require other dedicated samples. The headspace gas as the sole atmospheric sample is problematic for many reasons. The quantity of gas present within the sample tube volume is insufficient for many investigations, and there will be exchange between solid samples, headspace gas, and tube walls. Importantly, the sample tube materials and preparation were not designed for optimal Mars atmospheric gas collection and storage as they were not sent to Mars in a degassed evacuated state and have been exposed to both Earth's and Mars' atmospheres. Additionally, there is a risk of unconstrained seal leakage in transit back to Earth, which would allow fractionation of the sample (leak-out) and contamination (leak-in). The science return can be improved significantly (and, in some cases, dramatically) by adding one or more of several strategies listed here in increasing order of effectiveness and difficulty of implementation: (1) Having Perseverance collect a gas sample in an empty sample tube, (2) Collecting gas in a newly-designed, valved, sample-tube-sized vessel that is flown on either the Sample Fetch Rover (SFR) or the Sample Retrieval Lander (SRL), (3) Adding a larger (50-100 cc) dedicated gas sampling volume to the Orbiting Sample container (OS), (4) Adding a larger (50-100 cc) dedicated gas sampling volume to the OS that can be filled with compressed martian atmosphere.

Timothy D. Swindle↗
NASA NTRSDate not supplied

Stable Chlorine Isotope Measurements of Astromaterials Using the Cs-Sputter Negative Ion Source of an Accelerator Mass Spectrometer

The volatile element Cl can be lost during the formation and evolution of planetary bodies, leading to fractionation of its two stable isotopes 35Cl and 37Cl. Chlorine isotope variations (reported as δ37Cl in parts per thousand (‰) relative to Standard Mean Ocean Chloride, SMOC) [1] are documented to exceed 80‰ [2] between different lunar rock samples and have been variably interpreted as the fingerprint of degassing during accretion, magma ocean, or volcanic portions of lunar history[3,4].The large intersample and intrasample variations observed by both bulk isotope ratio mass spectrometry (IRMS) and in-situ secondary ion mass spectrometry (SIMS) methods are difficult to interpret in part because of a paucity of bulk Cl isotope measurements (Figure 1).This lack of high-precision bulk data is due to the relative rarity of IRMS laboratories capable of making these high precision measurements on small samples of precious planetary materials such as those returned by human or robotic exploration. Here we present a new method for performing high precision δ37Cl measurements using the Cs-sputter negative ion source of an existing accelerator mass spectrometer. A brief description of the methods used for this work is followed by the results of our δ37Cl measurements and a discussion of the technique’s possible applications.

Chlorine↗
NASA NTRSDate not supplied

From Source to Surface: An Investigation of Magmatic Lunar Volatiles

Lunar missions led by NASA discovered water ice on the Moon’s surface [1-3], revolutionizing views of the abundance, distribution, and potential sources of H2O and other volatiles. Volatiles play an important role in affecting the rheological properties of minerals and melts and influencing magma eruption processes. In order to determine the indigenous volatile inventory of the Moon, it is vital to identify the magmatic and secondary processes that may have affected the volatile contents in lunar minerals [4]. As part of the Apollo Next Generation Sample Analysis (ANGSA) program we are investigating the petrogenesis of a set of four Apollo lunar basalts collected from the rim of Steno Crater 71035, 71037, 71055, and specially curated sample 71036. Our team is studying the petrology in 2D and 3D (this work), chronology (Pomeroy et al., LPSC 2022), oxidation state of sulfur in apatite (Brounce et al., LPSC 2022), and volatile inventory of the sample set in order to understand the age and genetic relationships among the basalts, their magma ascent conditions and eruptive signatures, and their degassing and surface histories. Here we present the first detailed study of the 2D and 3D mineralogy, textures, 3D vesiculation, and chemistry of these basalts to shed light on their magmatic, volcanic, and post-eruptive histories. Note: Extended abstract on document.

Z. E. Wilbur↗
NASA NTRSDate not supplied

Lunar TLP's and the Tectonic Processes of the Earth and the Moon

We study the transient lunar phenomena (TLP) as an indicator of lunar tectonic. Seismic phenomena can be used as a direct indicator of some tectonic activities of the planets The Moon-Earth gravitational interaction has been studied extensively as a triggering mechanism to geodynamics. In this work, we study the reverse interaction Earth-Moon in relation to the TLP activities. The lunar outgassing potentially is the leading cause for TLP activities resulting from the lunar interior's dynamic mechanism. We have studied Earth venting and earthquakes processes and have found that radon was frequently activated before significant seismic events due to Moon-Sun interaction with Earth (Ouzounov et al., 2018). Earthquake lights, an associated phenomenon reported before some major earthquakes, are analog to TLP activities on the moon. In 1972, N. Kozyrev suggested a possible moon response to the significant seismic events on Earth. To understand whether TLP's activities have any possible connection with Earth geodynamics, we perform a statistical check between the significant seismic activities from the NEIC catalog and lunar TLPs for 1907-1977 for four lunar areas :Aristarchus, Plato, Gassendi, and Alphonsus. We use TLP compiled catalog based on Middlehurst et al. (1968), Cameron (2006a,b), and Crotts (2008) catalogs. Our results revealed a causal relationship between significant earthquakes and TLP events. However, this relation varies from the location and depth of the seismic events. Deformation triggers the degassing process, and TLPs are indicators for those underlying activities. Our work can provide new information about the origin of TLP and the existence of a possible relationship between the tectonic processes of Earth and the Moon.

D Ouzonov↗
NASA NTRS2022

VESIcal: An Open-source Thermodynamic Model Engine for Mixed Volatile (H2O-CO2) Solubility in Silicate Melts

Modeling the solubility of volatiles in silicate melts is fundamental to the interpretation of volcanic systems and has implications for magma dynamics, eruption style, and material transport between the mantle, crust, and atmosphere. Recent advancements in computational capabilities and access to computing tools has outpaced the functionality and extensibility of previously available modeling platforms. Here we present VESIcal (Volatile Equilibria and Saturation Index calculator), the first comprehensive modeling tool for H2O, CO2, and mixed (H2O-CO2) solubility in silicate melts that: a) allows users access to seven popular models, with easy inter-comparison between models; b) provides universal functionality for all models (e.g., functions for calculating saturation pressures, degassing paths, etc.); c) can process large datasets (1,000’s of samples) automatically; d) can output computed data into an Excel spreadsheet or CSV file for post-modeling analysis; e) integrates plotting capabilities directly within the tool; and f) provides all of this within the framework of a python library, making the tool extensible by the user and allowing any of the model functions to be incorporated into any other code capable of calling python.Here we will provide a demonstration of VESIcal and its capabilities with applications to various volcanic processes affected by volatiles. VESIcal represents the first tool capable of directly comparing multiple solubility models and equations of state. We find that commonly used models predict surprisingly different volatile solubilities, particularly for pure CO2 or mixed CO2-H2O fluids. Even for melt compositions that are well represented in the calibration datasets of multiple models (e.g., MORBs), calculated solubilities for pure CO2 and pure H2O can deviate from one another by factors of >2 leading to 2x deviations in calculated saturation pressures (e.g., 5 to 10 kbar). The solubility of CO2 predicted by different rhyolitic models also differs substantially, overwhelming other sources of uncertainty such as analytical errors on measurements of volatile contents or uncertainties in crustal density profiles. This highlights the importance of model choice when drawing geological conclusions based on volatiles in magmas.

Kayla Iacovino↗
NASA NTRSDate not supplied

Detecting Volcanic Co2 Emissions Hidden in Tropical Volcanic Forests Using Fixed-Wing sUAS

CO2 emissions are among the earliest indicators of subsurface state change and reactivation of volcanic systems and these deep signals reflect in faint diffuse emissions variations on volcanic flanks. Monitoring vast areas of rainforests covering tropical volcanoes is challenging, and space-borne sensors like OCO-2 are not sensitive enough. Fortunately, trees exposed to mild enhancements of CO2 may experience fertilization and build excess CO2 into excess biomass (Cawse-Nicholson, et al. 2018, Biogeosciences). They also process excess CO2 through photosynthesis, measurable by fluorescence (Bogue et al., 2019, Biogeosciences). Furthermore, spaceborne remote sensing instruments have demonstrated increasing NDVI months to years before eruptions, unexplained by other factors (e.g., Houlie et al. 2006, EPSL; Seiler et al. 2017, PLoS One). By providing a means to map large areas of above-canopy CO2 variations over tropical rainforest on the flanks of actively degassing volcanoes, we enable to interpret the signals plants provide in response to excess CO2 with airborne and spaceborne hyperspectral remote sensing methods, including a possible future Surface Biology and Geology (SBG) NASA satellite mission.As a critical step to mature and test this concept, we deployed small unmanned aerial systems (sUAS) using a fixed-wing sUAS designed for autonomous operations and long endurance in extreme environments, without causing significant disturbance of the sampled air. We integrated an in-situ sensor to record the CO2 enhancement field above the forest canopy. Test flight results on the flanks of Turrialba volcano in Costa Rica above forest canopies covering known moderate gas seeps demonstrate the sUAS-borne detection and mapping capabilities of above-canopy elevated CO2 gradients. The strong detection capabilities and high detector signal stability resulted from key system design elements including RF shielding, mechanical stabilization, and calibration procedures. This highly robust system is readily applied for diffuse volcanic CO2 emission studies on active volcanoes covered by dense vegetation.

Volcanic↗
NASA NTRSDate not supplied

Comparing Satellite Measurements of Volcanic SO2 Mass from OMI, OMPS and TROPOMI

Sulfur dioxide (SO2) is a major air pollutant that contributes to acid rain and aerosol formation (e.g., sulfates), adversely affects the environment and human health, and explosive volcanic SO2 emissions can impact climate. The majority of SO2 emissions are related to anthropogenic processes (e.g., fossil fuel burning, metal ore smelting operations), although natural processes such as volcanic eruptions and degassing also play an important role as anthropogenic SO2 emissions continue to decline. Generally, the most interest in volcanoes occurs during major eruptions. We will focus on comparing volcanic SO2 outgassing that occurs on an almost daily basis from lesser known volcanoes using satellite data. At NASA’s Global Sulfur Dioxide Monitoring Home page (https://so2.gsfc.nasa.gov/), we have been posting daily SO2 maps from 40 volcanic and industrial regions around the world using measurements from three satellite instruments; the Ozone Monitoring Instrument (OMI) onboard NASA’s Earth Observing System Aura satellite, the Ozone Monitoring and Profiler Suite (OMPS) onboard the NASA-NOAA Suomi National Polar-orbiting Partnership (NPP) satellite, and the TROPOspheric Monitoring Instrument (TROPOMI) onboard the ESA/Copernicus Sentinel-5 Precursor satellite. These instruments in low Earth sun-synchronous polar orbits with 1:30-2:00 pm equator crossing local time provide daily SO2 maps at different spatial resolutions: 13 x 24 km2, 50 x 50 km2 and 5.5 x 3.5 km2 for OMI, OMPS and TROPOMI respectively. Data from OMI are available since October 2004 (partial coverage since 2008), from OMPS since 2012 and from TROPOMI since 2018. We will present comparative SO2 mass time-series (see Hunga-Tonga plot) and statistical analyses of recent eruptions that have data from all the instruments.

SO2↗
NASA NTRSDate not supplied

A Chlorine Isotope Transect Across the Sudbury Impact Deposits Reveals Enigmatic Isotopic Fractionation

Volatile elements play an important role in a variety of cosmochemical and geochemical processes. As such, there has been significant interest in their abundance and isotopic composition. Chlorine is an important element for tracing these processes because it is incompatible in nearly all minerals, extremely volatile, and strongly hydrophilic [1]. The Cl isotope composition ( 37 Cl/ 35 Cl) of meteoritic components, therefore, can provide useful information regarding the isotopic reservoirs that were present in the early Solar System and any secondary processes that may have occurred on different parent bodies (e.g., [2-4]). There is a relatively narrow range in the Cl isotope compositions of terrestrial, Martian, and chondritic meteorites (δ 37 Cl ~ −6 to +4‰) (e.g., [2,3,5,6]), with exceptions to this being the Moon and Vesta (up to ~ +81‰ and ~ +40‰, respectively) [4, 5, 7-10]. One hypothesis for the extreme Cl isotope fractionation observed on the Moon is degassing following large-scale (possibly even crust-breaching) impact events [7-9]. The role of hypervelocity impacts and impact-generated magmatism in the isotopic evolution of planetary materials, however, has been until recently an area of limited published research with the majority of works focusing on the effects of impact shock (e.g., [10-13]). The ~ 1.85 Ga Sudbury impact crater [14] located in Ontario, Canada, is one of the three largest impact craters on Earth with good exposures of its impact melt sheet and overlying breccias [15,16]. The impact melt sheet, called the Sudbury Igneous Complex (SIC), is up to 5 km thick [17], with an estimated original volume of >10 4 km 3 [18], and differentiated. Recent work demonstrated evaporative loss and isotope fractionation of the moderately volatile element zinc and suggest melt sheets produced by impacts could have a significant effect on the Earth’s volatile inventory [19]. In this study we investigate the abundance and isotopic composition of Cl as well the water abundance of apatite from the SIC and the overlying crater-fill to test the hypothesis that large-scale impacts may have generated the extensive Cl isotopic fractionation observed on the Moon.

Sudbury↗
NASA NTRS2022

Out of the blue: volcanic SO e2 emissions during the 2021–2022 eruptions of Hunga Tonga – Hunga Ha'apai (Tonga)

Most volcanism on Earth is submarine, but volcanic gas emissions by submarine eruptions are rarely observed and hence largely unquantified. On January 15, 2022 a submarine eruption of Hunga Tonga-Hunga Ha'apai (HTHH) volcano (Tonga) generated an explosion of historic magnitude, and was preceded by ≈1 month of Surtseyan eruptive activity and two precursory explosive eruptions. We present an analysis of ultraviolet (UV) satellite measurements of volcanic sulfur dioxide (SO 2 ) between December 2021 and the climactic January 15, 2022 eruption, comprising an unprecedented record of Surtseyan eruptive emissions. UV measurements from the Ozone Monitoring Instrument (OMI) on NASA’s Aura satellite, the Ozone Mapping and Profiler Suite (OMPS) on Suomi-NPP, the Tropospheric Monitoring Instrument (TROPOMI) on ESA’s Sentinel-5P, and the Earth Polychromatic Imaging Camera (EPIC) aboard the Deep Space Climate Observatory (DSCOVR) are combined to yield a consistent multi-sensor record of eruptive degassing. We estimate SO 2 emissions during the eruption’s key phases: the initial December 19, 2021 eruption (≈0.01 Tg SO 2 ); continuous SO 2 emissions from December 20, 2021 – early January 2022 (≈0.12 Tg SO 2 ); the January 13, 2022 stratospheric eruption (0.06 Tg SO 2 ); and the paroxysmal January 15, 2022 eruption (≈0.4-0.5 Tg SO 2 ); yielding a total SO 2 emission of ≈0.60.7 Tg SO 2 for the eruptive episode. We interpret the vigorous SO 2 emissions observed prior to the January 2022 eruptions, which were significantly higher than measured in the 2009 and 2014 HTHH eruptions, as strong evidence for a rejuvenated magmatic system. High cadence DSCOVR/EPIC SO 2 imagery permits the first UV-based analysis of umbrella cloud spreading and volume flux in the January 13, 2022 eruption, and also tracks early dispersion of the stratospheric SO 2 cloud injected on January 15. The ≈0.4-0.5 Tg SO 2 discharged by the paroxysmal January 15, 2022 HTHH eruption is low relative to other eruptions of similar magnitude, and a review of other submarine eruptions in the satellite era indicates that modest SO 2 yields may be characteristic of submarine volcanism, with the emissions and atmospheric impacts likely dominated by water vapor. The origin of the low SO 2 loading awaits further investigation but scrubbing of SO 2 in the water-rich eruption plumes and rapid conversion to sulfate aerosol are plausible, given the exceptional water emission by the January 15, 2022 HTHH eruption.

Volcanoes↗
NASA NTRS2022

Development Towards Stable Chlorine Isotope Measurements of Astromaterials Using the Modified Middleton Source of an Accelerator Mass Spectrometer

The volatile element Cl can be lost during the formation and evolution of planetary bodies, leading to fractionation of its two stable isotopes 35Cl and 37Cl. Chlorine isotope variations (reported as δ37Cl in parts per thousand (‰) relative to Standard Mean Ocean Chloride, SMOC) are documented to exceed 80‰ between different lunar rock samples and have been variably interpreted as the fingerprint of degassing during accretion, magma ocean, or volcanic portions of lunar history. The large intersample and intrasample variations observed by both bulk isotope ratio mass spectrometry (IRMS) and in-situ secondary ion mass spectrometry (SIMS) methods are difficult to interpret in part because of a paucity of bulk Cl isotope measurements. This lack of high-precision bulk data is due to the relative rarity of IRMS laboratories capable of making these high precision measurements on small samples of precious planetary materials such as those returned by human or robotic exploration. Here we present a new method for performing high precision δ37Cl measurements using the modified Middleton ion source of an existing accelerator mass spectrometer. For samples with as little as 1 μg Cl–the equivalent of 2–4 mm3 of a typical lunar rock sample–the average cathode accuracy is ∼1‰. Cathode reproducibility is typically ∼1‰ (2σ) for samples with at least 10 μg of Cl, increasing to ∼3–6‰ for aliquots with ∼1–2 μg Cl, similar to published SIMS results and sufficient to study astromaterials from the Moon, Mars, or 4 Vesta, which have tens of ‰ observed variations.

Tyler S. Anderson↗
NASA NTRS2024

Constraining the Thermal and Textural Evolution of Evolved Achondrite DOM 10100: Implications for Volatile Loss

Identification of evolved achrondritic clasts suggests that some early planetesimals experienced extensive differentiation and formed chemically evolved crusts. Many of these samples contain volatile-bearing phases (i.e., apatite, merrillite, nominally anhydrous minerals), which can be used to constrain volatile budgets and abundancies via in-situ measurements. These ancient crustal rocks are subject to high heat, moderate pressures, potentially hot mineral-rich fluids, and degassing that has likely modified many of these volatiles, and their abundancies do not represent the composition of the primary magma from which these achondrites formed. In this work we attempt to deconvolve the thermal evolution of these samples to provide petrologic information that can be used for making inferences regarding their volatile history, and ultimately constraining volatile budgets on planetary bodies in the early Solar System. Here, we combine in-situ major element geochemistry, thermodynamic modeling, and detailed textural and microstructural observations to reconstruct the thermal and textural evolution of howardite DOM 10100, which contains a dacite within its matrix. Previous analyses of several sections of DOM 10100 suggest that the dacitic clast is evidence for partial melting of Vesta’s differentiated basaltic crust, making it an ideal candidate for evolved crustal studies. While its igneous petrogenesis has been well constrained, there is still opportunity to better characterize its post-crystallization thermal history, including possible thermal metamorphism and cooling.

J S Gorce↗
NASA NTRS2024

Variations in Apatite F, Cl, and OH Abundances in Primitive Achondrites: Evidence of Fractional Melting?

The apatite group minerals [Ca 5 (PO 4 ) 3 (F,Cl,OH)] are some of the primary mineralogical reservoirs for phosphorus on Earth and a common phosphate mineral within a broad range of extraterrestrial samples. Naturally occurring apatite hosts F, Cl, and OH as essential structural constituents, and all three make up the apatite endmembers fluorapatite, chlorapatite, and hydroxylapatite, respectively. Although apatite is one of the most common phosphate minerals in meteorites and rocks from Earth, it typically occurs at minor to trace abundances. Apatite has been widely used as a mineralogical tool to probe the interiors of both differentiated and undifferentiated parent bodies for information about volatiles; however, little work has been done on apatite F, Cl, and OH abundances of apatite from primitive achondrite meteorites. There are broad differences between apatite X -site chemistry in chondrite parent bodies (typically F-poor) compared to apatite from basaltic rocks from many achondrite parent bodies (Cl-poor, apart from Mars). These differences could indicate that planetary differentiation processes, namely melting, play an important role in the evolution of apatite X -site chemistry. In fact, some ordinary chondrite meteorites that exhibit evidence of minor impact melting have apatite with X -site compositions that are much more F-rich than typical chondrite apatite. McCubbin et al., hypothesized that the F-rich compositions of the apatite in ordinary chondrites affected by impact melting could be the result of apatite partially melting, driving the residual apatite to more F-rich compositions; however, they also indicated that degassing of the more volatile Cl and H may also contribute to the F-enrichment. To further test the partial melting hypothesis, we investigate the F, Cl, and OH (by difference) abundances of apatite from primitive achondrite parent bodies given that they are thought to come from partially differentiated parent bodies that represent residues after partial melting. Consequently, their apatites could provide valuable insights into the effects of melting on apatite X -site chemistry. In this study, we report F and Cl abundances of apatite from a broad array of primitive achondrite meteorites, and we develop a model for apatite fractional melting using known apatite-melt partitioning relationships. Together, we use these results to further elucidate the role of melting on apatite X -site compositions.

F M McCubbin↗
NASA NTRS2022

The H2o Content of the Ureilite Parent Body

The fate of highly volatile elements (H, C, F, Cl and S) during planetary accretion and differentiation is debated. Recent analyses of water in non-carbonaceous chondrites (RC, OC, EC) and achondrites (angrites, eucrites) have been used to argue that inner solar system parent bodies accreted and retained their highly volatile element budgets from their primary feedstock without substantial loss during accretion, metamorphism and differentiation. An alternative model posits that differentiated inner solar system parent bodies (e.g., the angrite parent body, 4 Vesta, Earth) derived the majority of their water from a carbonaceous chondrite-like source, delivered during the final stages of accretion. In order to add new constraints to this debate, we have measured water in nominally anhydrous minerals, melt inclusions, and interstitial glass in ureilites, the largest group of primitive achondrites in the terrestrial meteorite collection. Primitive achondrites did not experience global melting and homogenization. Therefore, these meteorites capture part of the transition from chondritic to achondritic parent bodies, allowing us to constrain the fate of water during the earliest stages of differentiation. Our nano-scale secondary ion mass spectrometry (nanoSIMS) analyses allow us to assess the viability of ureilite-like material as a potential source of terrestrial water. Analyses of pigeonite in main group ureilites yield a range of 2.0 – 6.0 µg/g H2O, and analyses of high-Ca pyroxene and glass (glassy melt inclusions and interstitial glass) in the Almahata Sitta ureilitic trachyandesite yield ranges of 13 – 19 µg/g H2O and 44 – 216 µg/g H2O, respectively. Mass balance, incremental melting, and batch melting calculations yield a preferred ureilite parent body H2O content of 2 – 20 µg/g, similar to previous estimates of water in the eucrite parent body (4 Vesta), but lower than estimates of Earth’s water budget. With these data, we demonstrate that 1) the ureilite parent body is H2O-depleted relative to the Earth; 2) ureilite-like material is unlikely to be a primary source of H2O to the Earth; 3) C and H are not necessarily coupled elements during planetary accretion and thermal processing; and 4) accretion, heating, partial melting, and degassing of rocky planetesimals likely results in significant depletion of H2O.

Primitive achondrites↗
NASA NTRSDate not supplied

A New Era of H-O-C-S Magma Solubility Modeling: Better, Faster, Stronger

H 2 O, CO 2 , and S are the most abundant volatiles in magmatic systems and are critical to understanding magma storage, phase equilibria, and volcanic eruptions. Models that consider all three of these components, however, may not allow for critical examination and adjustment of assumptions underlying the model, or provide benchmark testing or extensible interfaces. Thus, understanding why models produce different results can be challenging. We have gathered authors of established (D-Compress) and recent (VolFe, EVo, Sulfur_X, MAGEC) H-O-C-S volatile solubility models to work together to understand how and why our models diverge. We present a series of benchmark basalt degassing scenarios revealing that often understated model assumptions such as fO 2 buffer equations, fO 2 -Fe 3+ /ΣFe relationships, and even major element normalization routines have outsized effects on model results. All models consider S 2- and S 6+ melt species but with different approaches to sulfate/sulfide capacities, partition coefficients, and species fugacities, leading to divergence in the evolution of modeled gas compositions, melt S and Fe speciation, and fO 2 , with the extent of divergence depending on melt composition. Such scenarios enable meaningful intercomparison of existing models and lay the groundwork for a user-friendly yet powerful solubility modeling framework. Given our wealth of existing solubility literature, we suggest that the field of magmatic volatiles should focus now on the creation of modern tools and the modular implementation of existing model equations or methods, and that the evaluation of code usability, transparency, and benchmarking should be codified pillars of the peer-review process. As an example of such an endeavor, we present early work coupling these sulfur solubility models with VESIcal, an extensible and rigorously tested python library containing seven existing H 2 O-CO 2 solubility models. VESIcal includes the ability to extract, edit, and even interchange assumptions underlying any model. For example, users may combine or swap separately published H 2 O, CO 2 , and S models, as well as underlying model choices, such as Equations of State and redox models.

volatiles in magmas↗