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Surface-Enhanced X-Ray Fluorescence

Surface-enhanced x-ray fluorescence (SEn-XRF) spectroscopy is a form of surface- enhanced spectroscopy that was conceived as a means of obtaining greater sensitivity in x-ray fluorescence (XRF) spectroscopy. As such, SEn-XRF spectroscopy joins the ranks of such other, longer-wavelength surface-enhanced spectroscopies as those based on surface-enhanced Raman scattering (SERS), surface-enhanced resonance Raman scattering (SERRS), and surfaceenhanced infrared Raman absorption (SEIRA), which have been described in previous NASA Tech Briefs articles. XRF spectroscopy has been used in analytical chemistry for determining the elemental compositions of small samples. XRF spectroscopy is rapid and quantitative and has been applied to a variety of metal and mineralogical samples. The main drawback of XRF spectroscopy as practiced heretofore is that sensitivity has not been as high as required for some applications. In SEn-XRF as in the other surface-enhanced spectroscopies, one exploits several interacting near-field phenomena, occurring on nanotextured surfaces, that give rise to local concentrations of incident far-field illumination. In this case, the far-field illumination comes from an x-ray source. Depending on the chemical composition and the geometry of a given nanotextured surface, these phenomena could include the lightning-rod effect (concentration of electric fields at the sharpest points on needlelike surface features), surface plasmon resonances, and grazing incidence geometric effects. In the far field, the observable effect of these phenomena is an increase in the intensity of the spectrum of interest - in this case, the x-ray fluorescence spectrum of chemical elements of interest that may be present within a surface layer at distances no more than a few nanometers from the surface.

Anderson, Mark↗

Tektite origin by hypervelocity asteroidal or cometary impact: The quest for the source craters

Tektites are natural glasses that are chemically homogeneous, often spherically symmetrical objects several centimeters in size, and occur in four known strewn fields on the surface of the Earth: the North American, moldavite (or Central European), Ivory Coast, and Australasian strewn fields. Tektites found within such strewn fields are related to each other with respect to their petrological, physical, and chemical properties as well as their age. A theory of tektite origin needs to explain the similarity of tektites in respect to age and certain aspects of isotopic and chemical composition within one strewn field, as well as the variety of tektite materials present in each strewn field. In addition to tektites on land, microtektites (which are generally less than 1 mm in diameter) have been found in deep-sea cores. Tektites are classified into three groups: (1) normal or splash-form tektites, (2) aerodynamically shaped tektites, and (3) Muong Nong-type tektites (sometimes also called layered tektites). The aerodynamic ablation results from partial remelting of glass during atmospheric passage after it was ejected outside the terrestrial atmosphere and quenched from a hot liquid. Aerodynamically shaped tektites are known mainly from the Australasian strewn field where they occur as flanged-button australites. The shapes of splash-form tektites (spheres, droplets, teardrops, dumbbells, etc., or fragments thereof) are the result of the solidification of rotating liquids in the air or vacuum. Mainly due to chemical studies, it is now commonly accepted that tektites are the product of melting and quenching of terrestrial rocks during hypervelocity impact on the Earth. The chemistry of tektites is in many respects identical to the composition of upper crustal material.

Koeberl, Christian↗

Global organic and inorganic aerosol hygroscopicity and its effect on radiative forcing

The climate effects of atmospheric aerosol particles serving as cloud condensation nuclei (CCN) depend on chemical composition and hygroscopicity, which are highly variable on spatial and temporal scales. Here we present global CCN measurements, covering diverse environments from pristine to highly polluted conditions. We show that the effective aerosol hygroscopicity, κ, can be derived accurately from the fine aerosol mass fractions of organic particulate matter (ϵ org ) and inorganic ions (ϵ inorg ) through a linear combination, κ = ϵ org · κ org + ϵ inorg · κ inorg . In spite of the chemical complexity of organic matter, its hygroscopicity is well captured and represented by a global average value of κ org = 0.12 ± 0.02 with κinorg = 0.63 ± 0.01 as the corresponding value for inorganic ions. By showing that the sensitivity of global climate forcing to changes in κ org and κ inorg is small, we constrain a critically important aspect of global climate modelling.

54 ENVIRONMENTAL SCIENCES↗

Small field campaign: aerosol – ice formation closure pilot study. Final Report

Prediction of atmospheric ice formation from aerosol particles by heterogeneous nucleation represents one of the grand challenges in atmospheric science. Our insufficient predictive understanding of primary ice formation is the reason that climate models typically do not include heterogeneous ice nucleation with subsequent effects on climate uncertainty. Mixed-phase clouds, where supercooled water droplets and ice crystals coexist play globally an important role regulating climate. This is especially the case for the Arctic region that experiences the greatest warming due to climate change compared to other regions in the world. Immersion freezing initiated by ice-nucleating particles (INPs) in supercooled water droplets is recognized as the dominant primary ice formation pathway in mixed-phase cloud regimes. For this reason, it is crucial to evaluate our capability to predict immersion freezing for a given ambient aerosol population. The goal of this project is conducting a field-based pilot study at the U.S. DOE Atmospheric Radiation Measurement (ARM) user facility at Southern Great Plains (SGP) to evaluate our capability to predict the number concentration of aerosol particles that serve as INPs in the immersion freezing mode. Successful prediction of INP number concentrations is also termed “closure”. This field-observational approach represents a first-of-its kind attempt of an aerosol–ice formation closure study (AEROICESTUDY). Very few closure studies related to INPs have been conducted, and to our knowledge, none using robust size-resolved ambient aerosol composition measurements as a starting point. Achievement of aerosol–ice formation closure relies on our ability to characterize the ambient aerosol population with respect to particles size and composition and to determine INP number concentrations for specified freezing temperatures. This requires numerous online and offline instrumentation resulting in this pilot field campaign being a multi-institutional and community-collaborative effort. We chose the ARM SGP megasite for this first aerosol-ice formation closure pilot study due to its significant measurement capabilities available to obtain detailed physical characterization of the local aerosol population including size distribution, mass loading, and chemical composition of non-refractory aerosol particles. The overall objective of this project is to identify ice nucleation parameterizations that produce the most robust predictions of INP numbers and thus are best suited to be included in cloud and climate models. This objective includes the following goals for this field and laboratory-based project: i) What are the crucial aerosol physicochemical property measurements needed to accurately guide ice nucleation representations in models and long-term INP measurements? ii) What level of parameter details needs to be known to achieve aerosol–ice formation closure? iii) What are the leading causes for climate model bias in INP predictions? We found that the advances in our understanding of immersion freezing garnered over the last 20 years allowed us to yield partial and full closures of atmospheric immersion freezing from ambient aerosol particles. When the aerosol population is physicochemically complex and parameterizations for representative INP types are not yet available, we still struggle to accurately predict INP number concentrations. This project clearly demonstrates that with more laboratory and field measurements that are accompanied by particle composition analysis, the necessary datasets to achieve aerosol–ice formation closure for various locations will emerge, thus providing a robust foundation for guiding the representation of INPs in cloud and climate models.

54 ENVIRONMENTAL SCIENCES↗

Evolution of ore deposits on terrestrial planets

Ore deposits on terrestrial planets materialized after core formation, mantle evolution, crustal development, interactions of surface rocks with the hydrosphere and atmosphere, and, where life exists on a planet, the involvement of biological activity. Core formation removed most of the siderophilic and chalcophilic elements, leaving mantles depleted in many of the strategic and noble metals relative to their chondritic abundances. Basaltic magma derived from partial melting of the mantle transported to the surface several metals contained in immiscible silicate and sulfide melts. Magmatic ore deposits were formed during cooling, fractional crystallization and density stratification from the basaltic melts. Such ore deposits found in earth's Archean rocks were probably generated during early histories of all terrestrial planets and may be the only types of igneous ores on Mars. Where plate tectonic activity was prevalent on a terrestrial planet, temporal evolution of ore deposits took place. Repetitive episodes of subduction modified the chemical compositions of the crust and upper mantles, leading to porphyry copper and molybdenum ores in calc-alkaline igneous rocks and granite-hosted tin and tungsten deposits. Such plate tectonic-induced mineralization in relatively young igneous rocks on earth may also have produced hydrothermal ore deposits on Venus in addition to the massive sulfide and cumulate chromite ores associated with Venusian mafic igneous rock. Sedimentary ore deposits resulting from mechanical and chemical weathering in reducing atmospheres in Archean earth included placer deposits (e.g., uraninite, gold, pyrite ores). Chromite, ilmenite, and other dense unreactive minerals could also be present on channel floors and in valley networks on Mars, while banded iron formations might underlie the Martian northern plains regions. As oxygen evolved in earth's atmosphere, so too did oxide ores. By analogy, gossans above sulfide ores probably occur on Mars, but not submarine ferromanganese nodules and crusts which have precipitated in oxygenated seawater on earth.

Burns, R. G.↗

Development of critical molecular weight-property specifications for high performance polymers used as adhesives and composites

The polyimide resin, LARC-160, was prepared from diethyl-3, 3', 4,4'-benzophenone tetracarboxylate, ethyl-5-norbornene-2,3-dicarboxylate and Jeffamine AP-22. The imidization reactions of NE and BTDE were studied by HPLC, C-13-NMR and IR. NE imidizes slowly at 12 C; BTDE imidizes when the resin is heated above 100 C. Both imidization reactions proceed directly to the imide. Neither amic acid is present in significant quantities at any stage of the imidization reactions. The monomer mixture was stored at 12 C for periods up to 14 months. The effects of resin aging at this temperature on the chemical composition of the resin monomer mixture and the imidized polymer formed on curing were investigated. Aging the resin monomer mixture has the effect of partially advancing the imidization reaction. The average size of the cured polymer increases slightly with resin age.

Kranbuehl, D. E.↗

Machine Learning Chemical Guidelines for Engineering Electronic Structures in Half-Heusler Thermoelectric Materials

Half-Heusler materials are strong candidates for thermoelectric applications due to their high weighted mobilities and power factors, which is known to be correlated to valley degeneracy in the electronic band structure. However, there are over 50 known semiconducting half-Heusler phases, and it is not clear how the chemical composition affects the electronic structure. While all the n-type electronic structures have their conduction band minimum at either the Γ - or X -point, there is more diversity in the p-type electronic structures, and the valence band maximum can be at either the Γ -, L -, or W -point. Here, we use high throughput computation and machine learning to compare the valence bands of known half-Heusler compounds and discover new chemical guidelines for promoting the highly degenerate W -point to the valence band maximum. We do this by constructing an “orbital phase diagram” to cluster the variety of electronic structures expressed by these phases into groups, based on the atomic orbitals that contribute most to their valence bands. Then, with the aid of machine learning, we develop new chemical rules that predict the location of the valence band maximum in each of the phases. These rules can be used to engineer band structures with band convergence and high valley degeneracy.

36 MATERIALS SCIENCE↗

The importance of environmental conditions in reflectance spectroscopy of laboratory analogs for Mars surface materials

Reflectance spectra are presented here for a variety of particulate, ferric-containing analogs to Martian soil (Fe(3+)-doped smectites and palagonites) to facilitate interpretation of remotely acquired spectra. The analog spectra were measured under differing environmental conditions to evaluate the influence of exposure history on water content and absorption features due to H2O in these samples. Each of these materials contains structural OH bonded to metal cations, adsorbed H2O, and bound H2O (either in a glass, structural site, or bound to a cation). Previous experiments involving a variety of Mars analogs have shown that the 3 micron H2O band in spectra of palagonites is more resistant to drying than the 3 micron H2O band in spectra of montmorillonites. Other experiments have shown that spectra of ferrihydrite and montmorillonites doped with ferric sulfate also contain sufficient bound H2O to retain a strong 3 micron band under dry conditions. Once the effects of the environment on bound water in clays, oxides, and salts are better understood, the hydration bands measured via reflectance spectroscopy can be used to gain information about the chemical composition and moisture content of real soil systems. Such information would be especially useful in interpreting observations of Mars where subtle spatial variations in the strengths of metal-OH and H2O absorptions have been observed in telescopic and ISM spectra. We measured bidirectional reflectance spectra of several Mars soil analogs under controlled environmental conditions to assess the effects of moisture content on the metal-OH and H2O absorptions. The samples analyzed include chemically altered montmorillonites, ferrihydrite. and palagonites from Hawaii and Iceland. Procedures for preparation of the cation-exchanged montmorillonites, ferric-salt doped montmorillonites, and ferric oxyhydroxides are described in detail elsewhere.

Bishop, J.↗

The Earth Surface Mineral Dust Source Investigation: An Earth Science Imaging Spectroscopy Mission

The Earth Surface Mineral Dust Source Investigation, EMIT, is planned to operate from the International Space Station starting no earlier than the fall of 2021. EMIT will use visible to short wavelength infrared imaging spectroscopy to determine the mineral composition of the arid land dust source regions of the Earth to advance our knowledge of the radiative forcing effect of these aerosols. Mineral dust emitted into the atmosphere under high wind conditions is an element of the Earth system with many impacts to the Earth’s energy balance, atmosphere, surface, and oceans. The Earth’s mineral dust cycle with source, transport, and deposition phases are studied with advanced Earth System Models. Because the chemical composition, optical and surface properties of soil particles vary strongly with the mineral composition of the source, these models require knowledge of surface soil mineral dust source composition knowledge to accurately understand dust impacts on the Earth system now and in the future. At present, compositional knowledge of the Earth’s mineral dust source regions from existing data sets is uncertain as a result of limited measurements. EMIT will use spectroscopically derived surface mineral composition to update the prescribe boundary conditions for state-of-the-art Earth System Models. The EMIT-initialized models will be used to investigate the impact of direct radiative forcing in the Earth system that depends strongly on the composition of the mineral dust aerosols emitted into the atmosphere. These new measurements and related products will be used to address the EMIT science objectives and made available to the science community for additional investigations. An overview of the EMIT science, development, and mission is presented in this paper.

Green, Robert O.↗

Lunar resource surveys from orbit

The chemical composition of lunar soil and rocks is known now for nine surface sites, by analysis of returned samples. Three classes of silicate material, mare basalt, KREEP, and highland material (sometimes called ANT) have been identified as major components. Gamma-ray and X-ray instruments have mapped the Apollo 15 and 16 ground tracks for major elements, K, and Th. It is hoped that the Lunar Polar Orbiter will carry instruments capable of producing a chemical map of the entire moon. The most exciting possibility is that ice may exist in shadowed regions near the lunar pole.

Arnold, J. R.↗

Properties of Desert Sand and CMAS Glass

As-received desert sand from a Middle East country has been characterized for its phase composition and thermal stability. X-ray diffraction analysis showed the presence of quartz (SiO2), calcite (CaCO3), gypsum (CaSO4.2H2O), and NaAlSi3O8 phases in as-received desert sand and showed weight loss of approx. 35 percent due to decomposition of CaCO3 and CaSO4.2H2O when heated to 1400 C. A batch of as-received desert sand was melted into calcium magnesium aluminosilicate (CMAS) glass at approx. 1500 C. From inductively coupled plasma-atomic emission spectrometry, chemical composition of the CMAS glass was analyzed to be 27.8CaO-4MgO-5Al2O3-61.6SiO2-0.6Fe2O3-1K2O (mole percent). Various physical, thermal and mechanical properties of the glass have been evaluated. Bulk density of CMAS glass was 2.69 g/cc, Young's modulus 92 GPa, Shear modulus 36 GPa, Poisson's ratio 0.28, dilatometric glass transition temperature (T (sub g)) 706 C, softening point (T (sub d)) 764 C, Vickers microhardness 6.3 +/- 0.4 GPa, indentation fracture toughness 0.75 +/- 0.15 MPa.m (sup 1/2), and coefficient of thermal expansion (CTE) 9.8 x 10 (exp -6)/degC in the temperature range 25 to 700 C. Temperature dependence of viscosity has also been estimated from various reference points of the CMAS glass using the Vogel-Fulcher-Tamman (VFT) equation. The glass remained amorphous after heat treating at 850 C for 10 hr but crystallized into CaSiO3 and Ca-Mg-Al silicate phases at 900 C or higher temperatures. Crystallization kinetics of the CMAS glass has also been investigated by differential thermal analysis (DTA). Activation energies for the crystallization of two different phases in the glass were calculated to be 403 and 483 kJ/mol, respectively.

Desert sand↗

Research on lunar materials

Abstracts of 14 research reports relating to investigations of lunar samples are presented. The principal topics covered include: (1) optical properties of surface and core samples; (2) chemical composition of the surface layers of lunar grains: Auger electron spectroscopy of lunar soil and ground rock samples; (3) high frequency electrical properties of lunar soil and rock samples and their relevance for the interpretation of lunar radar observations; (4) the electrostatic dust transport process; (5) secondary electron emission characteristics of lunar soil samples and their relevance to the dust transportation process; (6) grain size distribution in surface soil and core samples; and (7) the optical and chemical effects of simulated solar wind (2keV proton and a particle radiation) on lunar material.

Gold, T.↗

Satellite Observations of the Effect of Natural and Anthropogenic Aerosols on Clouds

Our knowledge of atmospheric aerosols (smoke, pollution, dust or sea salt particles, small enough to be suspended in the air), their evolution, composition, variability in space and time and interaction with clouds and precipitation is still lacking despite decades of research. Understanding the global aerosol system is critical to quantifying anthropogenic climate change, to determine climate sensitivity from observations and to understand the hydrological cycle. While a single instrument was used to demonstrate 50 years ago that the global CO2 levels are rising, posing threat of global warming, we need an array of satellites and field measurements coupled with chemical transport models to understand the global aerosol system. This complexity of the aerosol problem results from their short lifetime (1 week) and variable chemical composition. A new generation of satellites provides exciting opportunities to measure the global distribution of aerosols, distinguishing natural from anthropogenic aerosol and measuring their interaction with clouds and climate.

Kaufman, Yoram J.↗

Hydrogen-Bonding Surfaces for Ice Mitigation

Ice formation on aircraft, either on the ground or in-flight, is a major safety issue. While ground icing events occur predominantly during the winter months, in-flight icing can happen anytime during the year. The latter is more problematic since it could result in increased drag and loss of lift. Under a Phase I ARMD NARI Seedling Activity, coated aluminum surfaces possessing hydrogen-bonding groups were under investigation for mitigating ice formation. Hydroxyl and methyl terminated dimethylethoxysilanes were prepared via known chemistries and characterized by spectroscopic methods. These materials were subsequently used to coat aluminum surfaces. Surface compositions were based on pure hydroxyl and methyl terminated species as well as mixtures of the two. Coated surfaces were characterized by contact angle goniometry. Receding water contact angle data suggested several potential surfaces that may exhibit reduced ice adhesion. Qualitative icing experiments performed under representative environmental temperatures using supercooled distilled water delivered via spray coating were inconclusive. Molecular modeling studies suggested that chain mobility affected the interface between ice and the surface more than terminal group chemical composition. Chain mobility resulted from the creation of "pockets" of increased free volume for longer chains to occupy.

Smith, Joseph G., Jr.↗

Evaluating the Structural Response of Amphiphilic Monolayers to Environmental Stimuli

Amphiphilic monolayers composed of end groups with distinct polar and nonpolar functional groups offer rapid and reversible interfacial adaptation in response to environmental stimuli such as a change in interfacial medium polarity. We have synthesized and characterized a suite of monolayers with functional groups of competing polarity designed to reconfigure their interfacial chemical composition in response to solvent polarity. In these films, the end group is designed to be able to reorient and expose the functional groups that minimize the interfacial free energy between the film and the environment. Using a combination of spectroscopic, computational, and wettability studies, we have investigated the responsive interfacial behavior of different end groups upon exposure to environments with varying polarities. Contact angle measurements across a series of polar and dispersive probe liquids reveal trends that reflect the underlying molecular flexibility and composition. Vibrational sum frequency generation (SFG) spectroscopy and atomistic molecular dynamics (MD) simulations confirm solvent-driven reorientation of the end groups, with restructuring observed at the interface. To quantify these effects, we have developed a surface energy calculation model that incorporates solvent-induced surface rearrangements into the estimations. Our findings reveal a strong dependence of surface energy and switching behavior on the length and flexibility of the functionalities in the end group, which affects the exposure of certain interfacial compositions under different solvents. These results offer new insights into the design of adaptive monolayers and provide a framework for evaluating solvent-responsive surfaces.

functional groups↗

The Arctic Boundary Layer Expedition (ABLE-3B): July - August 1990

The Arctic Boundary Layer Expedition (ABLE) 3B used data from ground-based, aircraft, and satellite platforms to characterize the chemistry and dynamics of the troposphere in subarctic and Arctic regions of midcontinent and eastern Canada during July - August 1990. This paper reports the experimental design for ABLE 3B and a brief overview of results. The detailed results are presented in a series of papers in this issue. The chemical composition of the atmospheric mixed layer over remote tundra, boreal wetland, and forested environments was influenced by emissions of CH4 and nonmethane hydrocarbons from biogenic sources, emissions of gases and aerosols from local biomass burning, and transport of pollutants into the study areas from urban/industrial sources. Minimum concentrations of both trace gas and aerosol species in boundary layer air were associated with Arctic source areas. In the free troposphere the biospheric influence was undetectable, and major sources of chemical variability were related to long-range transport of pollutants into the study areas from biomass burning and industrial sources in Alaska and the Great Lakes regions, respectively. Minimum concentrations of both trace gas and aerosol species in the free troposphere were associated with a persistent, widespread air mass which both chemistry and air mass trajectory analyses suggested had originated in the tropical Pacific. Subsidence of air from the upper troposphere and lower stratosphere frequently enhanced ozone and influenced other trace gas and aerosol species at midtropospheric altitudes. The North American Arctic is a complex dynamical and chemical environment with considerable spatial and temporal variability in aerosol and trace gas concentrations. The use of atmospheric chemical indicators for climate change detection will require a much more comprehensive Arctic monitoring program than currently exists.

Harriss, R. C.↗

Modeling and Observations of the Response of Tropical Tropospheric Ozone to ENSO

The El Nino-Southern Oscillation (ENSO) is the dominant mode of tropical variability on interannual time scales. ENSO appears to extend its influence into the chemical composition of the tropical troposphere, Recent results have revealed an ENSO induced wave-1 anomaly in observed tropical tropospheric column ozone, This results in a dipole over the western and eastern tropical Pacific, whereby differencing the two regions produces an ozone anomaly with an extremely high correlation to the Nino 3.4 Index. We have successfully reproduced this result using the Goddard Earth Observing System Version 5 (GEOS-5) general circulation model coupled to a comprehensive stratospheric and tropospheric chemical mechanism forced with observed sea surface temperatures over the past 25 years, An examination of the modeled ozone field reveals the vertical contributions of tropospheric ozone to the column over the western and eastern Pacific region, We will show targeted comparisons with SHADOZ ozonesondes over these regions to provide insight into the vertical structure. Also, comparisons with NASA's Aura satellite Microwave Limb Sounder (MLS) and Tropospheric Emissions Spectrometer (TES) instruments and other appropriate data sets will be shown. In addition, the water vapor response to ENSO will be compared to help illuminate its role relative to dynamics in impacting ozone concentrations. These results indicate that the tropospheric ozone response to ENSO is potentially a very useful chemistry-climate diagnostic and should be considered in future modeling assessments.

Oman, L. D.↗

VALENTInE: A Concept for a New Frontiers Class Long Duration In-Situ Balloon Mission to Venus

Venus and Earth are similar in bulk composition, size, density, and approximate distance from the Sun, yet Venus’s modern-day climate and surface geology is distinctly different [1]. Previous missions to Venus revealed unusual volcanic features, possible continental crust, widespread volcanic plains, a weak magnetic field [2], and insights into the Venusian atmosphere [3,4]. Unfortunately, data from these missions were limited in spatial and temporal resolution and global extent. A future mission to Venus is critical to address fundamental questions surrounding the chemical composition and dynamics of the Venusian atmosphere [5], its geologic history [6,7], its internal structure [8,9], and its habitability throughout time [10,11]. We present the Venus Air and Land Expedition: a Novel Trailblazer for In situ Exploration (VALENTInE) mission to meet this need. VALENTInE is a variable altitude balloon that will passively float in Venus’s atmosphere between 45 and 55 km altitude. VALENTInE will acquire atmospheric data at varying latitudes and longitudes in addition to mapping the surface geomorphology and mineralogy across multiple terrains. Mission Objectives: The VALENTInE mission concept is driven by four main science objectives: 1. Determine whether the driving force of the superrotation of Venus’s atmosphere is caused by horizontal or vertical momentum transport. 2. Determine whether the atmospheric composition and noble gas inventory of the Venusian atmosphere is a product of outgassing from the initial protoplanetary source or if there are significant contributions from exogenic sources. 3. Determine whether the tesserae regions (particularly Aphrodite Terra) are felsic and relatively older than surrounding regions. 4. Determine if there is any evidence of a recent dynamo preserved in the rock record of Venus. Mission Overview: A balloon architecture provides a robust system that can survive long-term in the Venusian environment while taking accurate measurements of the lower cloud deck and surface. Two prior balloon missions to Venus, VEGA 1 and VEGA 2 in 1984, have demonstrated the potential for such planetary exploration; however, these missions were short-lived (46 hr), with limited range (54 km). Our spacecraft concept consists of a battery powered balloon with a gondola and flyby carrier stage (Fig. 1). Our novel design allows for at least 15 days of atmospheric exploration, including multiple ascents and descents in the Venus atmosphere. VALENTInE is baselined to launch in 2032, cruise on solar power for 128 days, enter, descend, and inflate (EDI) into Venus’s atmosphere above Aphrodite Terra, and float in Venus’s atmosphere for a total nominal mission duration of 15 days. The balloon, able to control its altitude by changing its buoyancy, will make one full circumnavigation every 4–8 days and move poleward ~1 o latitude per day; it will be passively directed by the horizontal air currents on Venus. The balloon can only be controlled in the z direction, and the expected latitude range is ±10° from EDI. The balloon itself will be a tracer for atmospheric structures such as zonal winds [5, 12]. During the 15-day operational period, there will be five dips to 45 km for a compositional study of the lower atmosphere and geological and magnetic mapping of the surface. Dips are used to take images and measurements closer to the surface and to obtain in situ vertical atmospheric profiles between 45 and 55 km. Instruments: The VALENTInE instrument payload will allow for extensive study of the geology, atmosphere, and interior of Venus. The instrument suite consists of six instruments. The mission profile for each instrument is shown in Fig. 2. Lower Atmosphere Meteorology Analyzer (LAMA) is an atmospheric structure instrument consisting of a thermometer, barometer, and accelerometer to continuously measure temperature and pressure as a function of altitude, longitude, and latitude. TracE and Noble Gas Investigator (TENGI) is aneutral mass spectrometer used to sample the dense atmosphere. TENGI will operate continuously at 45 km and 55 km and will measure D/H ratios, as well as Ne, Ar, and O isotopic ratios. Kilometer Scale Spectral Imager (KSSI) is amultispectral imager (850-1150 nm) used to resolve surface features on the order of km. Near InfraRed Multispectral Photometer (NIRMP) is an Infrared (IR) photometer used to image the surface through the clouds to characterize mineral assemblages at five different areas of the surface. NIRMP will be operated during dwell. ELevation REConnaissance (ELREC) is a light detection and ranging (LIDAR) instrument used for measuring topography at five different areas of the surface. The ELREC data will be combined with those of NIRMP to determine mineral assemblages and how they correlate to topography. Magnetic Exploration and Interior Detective (MEID) is a magnetometer used to detect any near-surface magnetic anomalies. The magnetometer will continuously operate at all altitudes. Mission Design: The spacecraft’s propulsion system will have a wet mass of 930 kg and will be launched on an Atlas V rocket. The spacecraft will jettison the payload upon arrival in Venus’s atmosphere before decelerating to orbital velocity. Figure 2. Notional power-dip profile while the balloon is on the dayside. Risks and Challenges: Raising and lowering the spacecraft to dip beneath the haze layer require a large amount of energy. This issue was partly compensated by limiting the number of dips over the 15 day prime mission. Power needs for pumping helium are reduced by slowing the descent speed, which consequently increases spatial resolution of in situ measurements between 45 and 55 km. The main limitation for the duration of the mission is the need to carry 15 days’ worth of batteries. The bus experiences external Venusian temperatures ranging from ~27°C at 55 km altitude to ~110°C at 45 km altitude. These high atmospheric temperatures require thermal protection for the bus (instruments, electronics, and flight systems) during its descent, dwell at 45 km, and ascent. The bus is maintained at a mechanically safe temperature range of -10°C to 50°C using white external paint, multi-layer insulation (MLI), mechanical/thermal isolation (e.g. Ti, composites), and ~57 kg of Phase Change Materials (PCM). Images and spectra taken below the haze dominate the available data transmission regardless of the time spent at 45 km. Therefore, less time at the lower altitude mainly reduces the coverage of in situ measurements there. Further, we assumed an unrealistically low-density material for the helium storage tanks on the gondola. However, this issue is partially resolved if we were to jettison 75% of the spent helium storage tanks. After the entry process, the balloon volume remains mostly inflated and storage tanks are required only for reducing balloon volume in dipping to 45 km. This mission was planned against an expected New Frontiers 5 (NF5) cost cap of $1B, as the NF5 call had not yet been released. The mission we describe fits within the predicted cost cap if the flyby carrier stage, responsible for powering the spacecraft during cruise and for relaying in situ measurements back to Earth, can be contributed by another space agency. Acknowledgments: We thank the JPL Planetary Science Summer School, especially A. Nash, J. Scully, K. Mitchell, L. Lowes, and J. Armijo, and our mentors from JPL Team X. Thank you to our review panel for their insightful review. References: [1] Kane, S. et al. (2019) JGR:Ps, 124 , 2015–2028. [2] Phillips, J. L., & Russell, C. T. (1987). JGR: Space Physics , 92 (A3), 2253-2263. [3] Nakamura, M. et al. (2018) Earth Planets Space, 70 (1), 144. [4] Svedhem, H. et al. (2009) JGR:P 114 (E5). [5] Limaye et al. (2009) Decadal Survey White Paper . [6] Ivanov, M. and Head, J. (2011) PSS, 59 (13) , 1559-1600. [7] Smrekar, S. et al. (2018) Space Sci Rev, 214 (5), 88. [8] O’Rourke, J. et al. (2018) EPSL, 502 , 46-56. [9] O’Rourke J. et al. (2019) GRL , (46), 5768–5777 [10] Way, M. et al. (2016) GRL, 43 (16), 8376-8383. [11] Way, M. et al. (2020) JGR:P, 125 (5), e2019JE006276. [12] Preston, R. A. et al. (1986) Science, 231 (4744), 1414-1416.

Mission Concept↗