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Lunar Advanced Volatile Analysis Integration and Testing

The Regolith and Environment Science Oxygen and Lunar Volatile Extraction (RESOLVE) payload is part of Resource Prospector (RP) along with a rover and a lander that are expected to launch in 2020. RP will identify volatile elements that may be combined and collected to be used for fuel, air, and water in order to enable deeper space exploration. The Resource Prospector mission is a key part of In-Situ Resource Utilization (ISRU). The demand for this method of utilizing resources at the site of exploration is increasing due to the cost of resupply missions and deep space exploration goals. The RESOLVE payload includes the Lunar Advanced Volatile Analysis (LAVA) subsystem. The main instrument used to identify the volatiles evolved from the lunar regolith is the Gas Chromatograph-Mass Spectrometer (GC-MS). LAVA analyzes the volatiles emitted from the Oxygen and Volatile Extraction Node (OVEN) Subsystem. The objective of OVEN is to obtain, weigh, heat and transfer evolved gases to LAVA through the connection between the two subsystems called the LOVEN line. This paper highlights the work completed during a ten week internship that involved the integration, testing, data analysis, and procedure documentation of two candidate mass spectrometers for the LAVA subsystem in order to aid in determining which model to use for flight. Additionally, the examination of data from the integrated Resource Prospector '15 (RP' 15) field test will be presented in order to characterize the amount of water detected from water doped regolith samples.

In-Situ Resource Utilization↗

Assessment of Volatile Depletion Mechanisms for the Moon - Pre-Cursors, Giant Impact, Core Formation, Post-Impact Loss

The volatile element depletions in the Moon have been recognized for decades. Multiple explanations have been debated, and arguments have become more quantitative, in large part due to new elemental partitioning and isotopic data. Depletions in pre-cursor materials and due to post-accretion degassing have been evaluated using isotopic data. Partitioning of many volatile elements into metallic cores can now be evaluated for many volatile siderophile elements (VSE). Here is presented an evaluation of the role of core formation for 12 volatile siderophile elements for which partitioning data is now available. Examination of all 12 elements at once allows recognition of general trends, without undue focus on one element. Ga, Ge, Zn, Sn, As, Sb, Cd, Ag, Bi, P, In, Cu are all moderately to highly volatile, and will be discussed in their order of volatility as gauged by their 50 percent condensation temperature.

Righter, K.↗

A Tale of "Two" Comets: The Primary Volatile Composition of Comet 2P/Encke Across Apparitions and Implications for Cometary Science

The highly favorable 2017 apparition of 2P/Encke allowed the first comprehensive comparison of primary volatile abundances in a given comet across multiple apparitions. This apparition offered opportunities to address pressing questions in cometary science, including investigating evolutionary and/or heliocentric distance (R(sub h)) effects on volatile production, sampling the hypervolatiles CO and CH4 in an ecliptic comet, and measuring volatile release at small R(sub h). The faintness and frequently low geocentric velocity of ecliptic comets during most apparitions make our near-infrared observations of these hypervolatiles rare and of high scientific impact. We characterized the volatile composition of 2P/Encke on three post-perihelion dates using the iSHELL spectrograph at the NASA Infrared Telescope Facility on Maunakea, HI. We detected fluorescent emission from nine primary volatiles (H2O, CO, C2H6, CH3OH, CH4, H2CO, NH3, OCS, and HCN) and three fragment species (OH*, NH2, and CN), and obtained a sensitive upper limit for C2H2. We report rotational temperatures, production rates, and mixing ratios (abundances relative to H2O). Compared to mean abundances in comets observed to date in the near-infrared, mixing ratios of trace gases in 2P/Encke were depleted for all species except H2CO and NH3, which were “normal.” The detection of the hypervolatiles CO and CH4 is particularly notable given the paucity of measurements in ecliptic comets. We observed significant differences in primary volatile composition compared to published pre-perihelion results from 2003 at larger R(sub h). We discuss possible mechanisms for these differences and discuss these results in the context of findings from the Rosetta mission and ground-based studies of comets.

Roth, Nathan X.↗

Volatiles Investigating Polar Exploration Rover (VIPER)

VIPER is a lunar volatiles detection and measurement mission that will be launched as a payload on the CLPS (Commercial Lunar Payload Services) provided Astrobotic's Griffin lander to the lunar south polar region. VIPER includes a suite of rover-mounted instruments that will conduct science and map volatiles (especially hydrogen-bearing volatiles). The VIPER rover is also designed to excavate volatiles such as hydrogen, oxygen, and water from the Moon. After landing the VIPER rover will travel to investigate a range of Ice Stability Regions (ISRs) across scales from 100s of meters to kilometers and conduct surface and subsurface assessment of lunar water and other volatiles. The VIPER science mission team will use the instrument data to characterize the nature of the volatiles in the area and to extrapolate these data to create global lunar water resource maps. The expected lunar surface mission duration is up to four lunar days, with active surface operations during the periods when both Sun exposure and direct to Earth (DTE) communication conditions overlap. When comm and Sun are not both available, VIPER will go into ‘Safe Haven operations’ and maintain survival temperatures until Sun and comm return. The rover is controlled in near-real time and science decisions are made both tactically (short-term) and strategically (longer-term) to achieve the mission science success criteria and objectives.

Anthony Colaprete↗

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↗

The Relationship Between Volatile Element Abundances and Iron Carrying Capacity in Lunar Volcanic and Impact Vapors

The highly volatile elements (e.g. H, C, S, Cl) released during lunar volcanism provide important insights into the bulk volatile composition of the Moon. Once erupted, some fraction of the species containing these elements may have migrated to the poles where they could have become sequestered in shadowed cold traps such as those found near the lunar South pole. The volatiles trapped in the lunar South pole are of great interest to the upcoming Artemis missions, which will be operating nearby and could sample some of those materials. Volcanic vapor deposits in the polar regions might also be supplemented by volatiles from other sources both exogenous (i.e. comets) and endogenous (i.e. remobilization of lunar volatiles by impact). Characterizing these endogenous sources is challenging because the highly volatile elements often leave little trace behind in the rocks themselves, which are inherently refractory by nature. Minerals are found on vug, vesicle, or fracture surfaces that have characteristics consistent with phases formed via direct deposition of a vapor, as opposed to crystallization from a liquid or via solid state decomposition. One common vapor-deposited species is metallic Fe, typically observed as subhedral to euhedral crystals found on vug or vesicle walls in mare basalts and on select breccia clast surfaces in regolith soil samples returned from the Moon. A particularly striking example is seen below in Fig. 1, where numerous Fe crystals are deposited onto the wall of a vug in Apollo 17 basalt sample 71036. Euhedral Fe crystals are not very common in Apollo breccia samples, though this may be from the limited number of systematic searches that have been performed. However, when Fe crystals are found, they can occur in extremely high abundance(e.g., sample 15402 which was specifically selected because of its numerous Fe crystals, was found to have a clast with 477 euhedral Fe crystals in a 570 x 570 μm area). What struck us as interesting about this was not only that it takes a large amount of Fe to make these crystal-rich deposits, but also that these crystal-rich deposits are not ubiquitous, and therefore they must be controlled by some aspect of their depositional conditions that varies. Since those conditions are inherently difficult to investigate and are critically interesting, we used thermochemical modeling as a tool to investigate the relationship between vapor-deposited Fe and various intensive and extensive parameters. We assumed that a high abundance of Fe in the vapor is required to form these crystals, thus the mass of Fe in the vapor was used to determine the plausibility of the vapor-deposited, euhedral Fe crystals observed in Apollo samples.

thermodynamics↗

Resource Prospector: A Lunar Volatiles Prospecting and ISRU Demonstration Mission

A variety of recent observations have indicated several possible reservoirs of water and other volatiles. These volatiles, and in particular water, have the potential to be a valuable or enabling resource for future exploration. NASA's Human Exploration and Operations Mission Directorate (HEOMD) Advanced Exploration Systems (AES) is supporting the development of Resource Prospector (RP) to explore the distribution and concentration of lunar volatiles prospecting and to demonstrate In-Situ Resource Utilization (ISRU). The mission includes a NASA developed rover and payload, and a lander will most likely be a contributed element by an international partner or the Lunar Cargo Transportation and Landing by Soft Touchdown (CATALYST) initiative. The RP payload is designed to: (1) locate near-subsurface volatiles, (2) excavate and analyze samples of the volatile-bearing regolith, and (3) demonstrate the form. extractability and usefulness of the materials. RP is being designed with thought given to its extensibility to resource prospecting and ISRU on other airless bodies and Mars. This presentation will describe the Resource Prospector mission, the payload and measurements, and concept of operations

In-Situ Resource Utilization (ISRU)↗

Spillage of Lunar Polar Crater Volatiles onto Adjacent Terrains: The Case for Dynamic Processes

We present an investigation of the release and transport of lunar polar crater volatiles onto topside regions surrounding the cold traps. The volatiles are liberated via surface energization processes associated with the harsh space environment, including solar wind plasma sputtering and impact vaporization. We find that some fraction of these volatiles can migrate from crater floors onto topside regions (those regions directly adjacent to and above the polar crater floors), and that these surrounding terrains should contain a sampling of the material originating within the crater itself. It is concluded that the nature of the volatile content on crater floors can be obtained by sampling the surface volatiles that have migrated or "spilled out" onto the adjacent terrain. This "spillage" effect could make human or robotic prospecting for crater resources significantly easier, since an assessment may not require direct entry into the very harsh polar crater environment. We also suggest that there are dynamic processes actively operating on the crater floors, and we estimate their source rates assuming dynamic equilibrium of the observed water frost and our modeled loss rates.

Vaporization↗

Modification of Caloris ejecta blocks by long-lived mass-wasting: A volatile-driven process?

The Caloris basin is the largest well-preserved impact basin on Mercury. As such, Caloris ejecta afford us an opportunity to study material from Mercury's deep interior with remote sensing. We have made observations of the geomorphology, colour, distribution, and flank slopes of the circum-Caloris knobs. Our observations suggest that these circum-Caloris knobs are modified ejecta blocks from the Caloris impact. High-resolution MESSENGER images show that knobs are conical and relatively uncratered compared with the surrounding plains, which implies the knobs have undergone resurfacing. We have observed material that has sloughed off knobs superposing impact craters that demonstrably postdate the Caloris impact, which requires some knob modification to have been more recent. We have observed hollows, depressions in Mercury's surface generally believed to have been caused by volatile-loss, on and closely associated with several knobs, which indicates that many knobs contain volatile material and that knob modification could extend into Mercury's recent past. Our measurements show that knob flanks typically have slopes of ∼21°, which is steep for a mound of unconsolidated material that was originally emplaced ∼3.8 Ga. The conical shape of knobs, their steep slopes, the dearth of superposed craters on knobs, and knob superposition relationships with other landforms suggest that Caloris ejecta blocks of arbitrary original shape were modified into their present shapes by long-lived mass-wasting. Mass-wasting must have dominated over impact gardening, which would have produced domal morphologies only. We suggest that mass-wasting was probably driven by volatile-loss, in a manner analogous to terrestrial landforms called ‘molards’. If the circum-Caloris knobs are analogous to molards, then they represent a landform and a process hitherto undocumented on Mercury, with implications for the volatile content of the planet's interior. These knobs therefore are prime targets for BepiColombo, which could search for fresh failures and volatile exposures in the knobs.

Mercury; Caloris basin; impact ejecta; volatiles; ↗

Application of Long-Path Gas Cell Assisted Infrared Spectroscopy for Detection of Lunar Volatiles and Advanced Curation Efforts

The motivation behind analyzing gaseous samples from the Permanently Shadowed Regions (PSRs) on the lunar surface is built upon the volatiles observed during the LCROSS mission. Advanced curation techniques under cold conditions are essential to the critical scientific analysis of these returned samples. The detection of various volatiles in returned samples by gas-phase infrared (IR) spectroscopy is known to be a powerful tool to understand the resources present in planetary bodies and Astro-materials. The identification and quantification of volatile compounds in returned planetary samples and regolith simulants by advanced and custom-built analytical devices are areas of primary research interest in our group and the Planetary Exploration & Astromaterials Research Laboratory (PEARL) facility. In this context, we discuss recent advancements and experimental results for quick analysis of the major volatiles detected by the LCROSS (water, CO 2 , CH 3 OH, and NH 3 ) by a long-path gas cell/FTIR (Fourier Transform Infrared) spectrometer system. The applicability of this system is demonstrated by qualitative analysis of a series of volatiles measured individually. In addition, the linear dependence of absorption intensity on headspace sample volumes was checked by measuring gas-phase IR absorption spectra of increasing volumes of pure CO 2 gas aliquots. Finally, the instrument performance was evaluated by measuring the relative concentration of NH 3 (g) in methanol solution.

Curation↗

Face‐on Orientation Matches Vertical Organic Electrochemical Transistors for High Transconductance and Superior Non‐Volatility

Abstract The recently developed vertical structure of organic electrochemical transistors (OECTs) can integrate volatile and non‐volatile functions into one reconfigurable device, making it highly promising. However, comparing with the conventional planar OECT (c‐OECT), the understanding of vertical OECT (v‐OECT) working principles and device engineering strategies is still lacking, impeding rational optimization. Since a major difference between c‐ and v‐OECTs is their charge transport directionality, which is highly influenced by crystallite orientations, the orientation–device structure match thus becomes an important yet outstanding topic for OECTs. Herein, using ann‐type small molecule IDIC‐MEG, investigate how much impact such match can have on OECT performance. The IDIC‐MEG c‐OECT fails to work due to the seriously hindered in‐plane electron transport by face‐on orientation. Surprisingly, simply changing the device structure from planar to vertical allows the resultant v‐OECT to exhibit the highest reported transconductance (46.3 mS) among all small‐molecule OECTs, thanks to the match between face‐on orientation and the vertical structure. Such match also leads to excellent non‐volatility, including highly predictable programmability and good operational stability. This work, for the first time, explicitly demonstrates the significance of orientation–device structure match for OECT optimization, establishing new guidelines for achieving high‐performance volatile and non‐volatile OECTs.

Chemistry↗

Nickel-rich, volatile depleted iron meteorites: Relationships and formation processes

Ungrouped iron meteorites Tishomingo, Willow Grove, and Chinga, and group IVB iron meteorites, are Ni-rich. Similarities include enrichments of 10–100 × CI for some refractory siderophile elements, and equivalent depletions in more volatile siderophile elements. Superimposed on the overall enrichment/depletion trend, certain siderophile elements (P, W, Fe, Mo) are depleted relative to elements of similar volatility. All three ungrouped irons derive from parent bodies formed in the early Solar System. Willow Grove and Chinga are characterized by cosmic ray exposure corrected 182 W/ 184 W consistent with metal-silicate segregation on their parent bodies within 1–3 Myr of Solar System formation, within the age range determined for segregation of magmatic iron meteorite parent bodies, including group IVB irons. Tishomingo is characterized by a younger model age 4–5 Myr subsequent to Solar System formation, reflecting either late stage melting resulting from 26 Al decay, or an impact resetting. The discovery of stishovite in Tishomingo, indicating exposure to a minimum shock pressure of 8–9 GPa, is consistent with the latter. Stishovite in Tishomingo and chromite included in troilite-daubréelite in IVB irons allows oxygen isotopic composition comparison between these meteorites. Different mass independent oxygen isotopic compositions of IVB irons and Tishomingo indicate genetically distinct parent bodies. By contrast, mass independent Mo isotopic compositions overlap within analytical uncertainties, indicating a similar, carbonaceous chondrite (CC) type genetic heritage. Molybdenum and 183 W isotopic data for Chinga and Willow Grove indicate derivation from CC type parent bodies. Willow Grove shares Mo and 183 W isotopic compositions with the Ni-rich South Byron Trio (SBT) grouplet and the Milton pallasite. These Ni-rich meteorites likely formed in the same general nebular environment as other CC planetesimals, likely the outer Solar System. Highly siderophile element (HSE) abundances of Willow Grove and Tishomingo are similar to some IVB meteorites, consistent with formation by moderate degrees of fractional crystallization from initial metallic melts with low S and P, and modestly fractionated HSE. The comparable HSE abundances of Tishomingo and Willow Grove to some IVB irons, yet substantially higher Ni concentrations, indicate formation on parent bodies with lower bulk HSE abundances or HSE concentration in proportionally smaller volumes of metal. HSE abundances in Chinga are considerably lower than in IVB irons, highly fractionated, and processes responsible for these remain elusive. For IVB irons and these ungrouped irons, high temperature condensation likely dominated the enrichment and depletion of the refractory and volatile siderophile elements, respectively. Parent body degassing may have also played a role. Relative depletion of volatile siderophile elements is not, however, a universal feature of high-Ni meteorites. The SBT and Milton pallasite are Ni-rich, but less depleted in the more volatile siderophile elements. Nickel enrichment was likely driven by oxidation of Fe metal during parent body accretion or core segregation. Oxidation of the Tishomingo and Willow Grove parent bodies may have occurred at ~ IW + 1, indicated by relative Mo and W depletions due to metal/water reaction during differentiation. Late-stage reduction, indicated by the presence of Cr-bearing sulfides in Tishomingo and IVB irons, may have resulted from exhaustion of the oxidant.

36 MATERIALS SCIENCE↗

Volatile traits expand the microbial playbook

Microbial metabolic functions are increasingly conceptualized as fitness-regulating traits. However, volatile compounds (the volatilome), despite their key roles in metabolism and ecology, are often overlooked in trait-based frameworks. We propose that volatile traits not only reflect ecological strategies but also shape them by mediating responses to selection pressures. Their volatility affects diffusion, substrate access, and interactions across space, conferring selective advantages as resources or waste products. We outline approaches to incorporate volatile traits into predictive models to improve understanding of microbial selection and community dynamics. Furthermore, this integration enables a more holistic view of microbial life by accounting for the ecological and evolutionary consequences of volatile-mediated processes.

54 ENVIRONMENTAL SCIENCES↗

The origin of volatile elements in the Earth–Moon system

Significance Understanding the history of volatile species such as water in the Earth–Moon system is a major objective of planetary science. In this work, we use the moderately volatile element Rb, which has a long-lived isotope ( 87 Rb) that decays to 87 Sr, to show that lunar volatile element depletion was not caused by the Moon-forming impact. The Rb–Sr systematics of lunar rocks mandate that the bodies involved in the impact that formed the Earth–Moon system were depleted in volatile elements relative to the bulk solar system prior to the impact. As such, Earth’s relatively small proportion of water is either primarily indigenous or was added after the Giant Impact from a source that contained essentially no moderately volatile elements.

58 GEOSCIENCES↗

High Semi-Volatile Organic Aerosol Contributions Associated with Ammonium Nitrate in the Coastal Urban Environment

Organic components often contribute 50% or more of the submicron aerosol mass in coastal urban environments, but their partitioning between the gas and particle phases is controlled by a complex mixture of unidentified organic compounds that are poorly constrained by observations. This study compares daily filter organic functional groups (OFG) with online organic mass fragments from La Jolla, California, as part of the Eastern Pacific Cloud Aerosol Precipitation Experiment (EPCAPE), quantifying the contributions of four types of non-volatile (NV) organic emission sources to the submicron composition. Daily filters retained only 0.79–0.98 µg/m3 NV submicron organic mass concentration, even though 1.8–1.9 µg/m3 non-refractory (NR) submicron organic mass concentration was measured online. The 62–64% of measured NR submicron organic mass concentration that exceeded what remained on the filters after 23-hr sampling is interpreted as semi-volatile, consistent with the moderate correlation of the NR NV difference to NR ammonium, NR nitrate, and biomass burning-related NV and NR organic factors. The association between semi-volatile organic components and ammonium nitrate likely results from both co-emission and co-evaporation. Size-resolved filter analysis showed that NV organic mass concentration accounts for 68% of NR organic mass concentration for 0.5–1 µm dry diameter but account for 9.0% for 0.18–0.5 µm dry diameter showing the differences in volatility between particle modes. Importantly, volatility of organic components was size-dependent Information Classification: General and associated with ammonium nitrate and biomass burning, providing guidance for constraining atmospheric aerosol properties in global models.

Pelayo, Christian↗

Volatiles in Chainpur chondrules

A study of volatile element concentrations in individual chondrules in the Chainpur LL3 chondrite is presented. Volatile elements differing in geochemical behavior tended to vary randomly and correlated variations were observed only for those elements inferred to occupy similar mineral sites. Variations in Co and Ni in kamacite show that metal in chondrule interiors has not approached equilibrium, and that postformational element distribution has mainly altered siderophile concentrations in surface metal grains, and has probably left ionic species unaltered. Etching to remove 3 to 5% of the chondrule dissolved siderophiles, enhanced Zn and Na volatiles relative to nonvolatile Cr in the etch, and produced a large Cd enhancement. If metamorphic redistribution of nonsiderophile volatiles was neglible, their high concentrations are inconsistent with chondrule formation by direct condensation, and models involving sudden melting of preexisting solids can explain the observations but require rapid cooling to prevent volatile loss.

Grossman, J. N.↗

Magmas as Selective Filters of Volatiles Between Planetary Mantles and Surfaces

The composition of early planetary atmospheres and biospheres which is a knowledge of the relationship between mantle volatiles and volcanic gases was analyzed. In the case of Earth it appears that volcanic rocks and gases are relatively oxidized compared to the upper mantle. In the case of the C-O-H volatiles, (H2O, CO2, CO, CH4, H2) the volcanic gases are enriched in H2O and CO2 while the volatiles in the mantle may be dominated by H2O, H2 and possibly CH4. An experimental technique was perfected for phase equilibrium studies in the 5-30 kbar range which allows accurate control of volatile species activities in the fluid phase. The system was used to measure the relative solubilities of H2O, CO2, CO, CH4 and H2 in magmas at 10 kbar pressure. It is found that mantle magmas will selectively screen volatiles from planetary surfaces, forcing volcanic gases towards the neutral QFM oxidation state where H2O is the dominant species.

Holloway, J. R.↗

Volatile degassing of basaltic achondrite parent bodies Evidence from alkali elements and phosphorus

The Na, K, Rb, Cs, and P abundances in eucrites, diogenites, basaltic clasts from polymict eucrite, howardites, and mesosiderites are examined, and compared with an average of highly incompatible refractory (AHIR) elements normalized to cosmic abundances. It is observed that basaltic eucrites and basaltic clasts show a positive correlation between K, Rb, and Cs, and alkali element/AHIR ratios; the volatile loss of the alkali elements from the basalt affects the parent body inventory of volatile elements. The data reveal that for diogenites, the alkali /AHIR ratios are 1.4-2 times greater than in basaltic eucrites and are more variable; and the negative relation between K, Rb, Cs, and the alkali/AHIR ratio correlate with progressive alkali loss through volatile outgassing during crystallization of one or more magmas resulting in a greater than 90 percent loss of the volatile element inventory from the parent body. It is also detected that P displays volatile loss from the basaltic eucrites and elevated P/AHIR ratios in diogenites.

Mittlefehldt, David W.↗