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NASA NTRS2001

Microcalorimetry: The First Two Decades

Our group at GSFC began experimental and theoretical work on microcalorimetry almost twenty years ago, in August of 1982. Over the next 10 months, we completed the initial demonstration of a Si impurity thermometer-based calorimeter as an X-ray spectrometer. This successful demonstration resulted in the development by many investigators of scientific applications for microcalorimeters, ranging from optical spectroscopy to dark matter detection to particle physics applications. Many new technical approaches for cryogenic detectors were proposed by investigators and have been developed. In this presentation, I will describe the early development of microcalorimeters at GSFC and University of Wisconsin and the subsequent rapid growth of this work around the world The key milestones in the early development were the initial spectroscopy demonstrations and the selection of XRS, our microlcalorimeter-based instrument for the Advanced X-ray Astrophysics Facility (AXAF) and ultimately for ASTRO-E. An additional key event was the development of the direct detection of dark matter experiment and the formation of the Center for Particle Astrophysics. Both of these programs provided long term support for this technology in its precarious early days. A major additional technical step in the development of detectors was the demonstration of devices based on superconducting transition edge sensors (TES). These detectors promised (and have delivered) improved energy resolution and higher event rate capabilities. They couple naturally to SQUIDS, which operate well at the low temperatures where the detectors must operate. The past two decades have taken microcalorimeters from their infancy to applications in real experiments. I will provide an overview of the early development of the devices and review the breadth of the present technology and applications.

Moseley, Harvey↗

DOE OSTI2025

Axion pulsarscope

Electromagnetic fields surrounding pulsars may source coherent ultralight axion signals at the known rotational frequencies of the neutron stars, which can be detected by laboratory experiments (e.g., pulsarscopes). As a promising case study, we model axion emission from the well-studied Crab pulsar, which would yield a prominent signal at 𝑓 ≈ 29.6 Hz regardless of whether the axion contributes to the dark matter abundance. We estimate the relevant sensitivity of future axion dark matter detection experiments such as DMRadio-GUT, Dark SRF, and CASPEr, assuming different magnetosphere models to bracket the uncertainty in astrophysical modeling. For example, depending on final experimental parameters, the Dark SRF experiment could probe axions with any mass 𝑚 𝑎 ≪ 10 −13 eV down to 𝑔 𝑎⁢𝛾⁢𝛾 ∼3 × 10 −13 GeV −1 with one year of data and assuming the vacuum magnetosphere model. These projected sensitivities may be degraded depending on the extent to which the magnetosphere is screened by charge-filled plasma. The promise of pulsar-sourced axions as a clean target for direct detection experiments motivates dedicated simulations of axion production in pulsar magnetospheres.

axions↗

NASA NTRS1994

Baryonic dark clusters in galactic halos and their observable consequences

We consider the possibility that approximately 10% of the mass of a typical galaxy halo is in the form of massive (approximately 10(exp 7) solar masses), compact (escape speeds approximately 100 km/s) baryonic clusters made of neutron stars (approximately 10% by mass), black holes (less than or approximately equal to 1%) and brown dwarfs, asteroids, and other low-mass debris (approximately 90%). These general properties are consistent with several different observational and phenomenological constraints on cluster properties subject to the condition that neutron stars comprise approximately 1% of the total halo mass. Such compact, dark clusters could be the sites of a variety of collisional phenomena involving neutron stars. We find that integrated out to the Hubble distance approximately one neutron star-neutron star or neutron star-black hole collision occurs daily. Of order 0.1-1 asteroid-neutron star collisions may also happen daily in the halo of the Milky Way if there is roughly equal cluster mass per logarithmic particle mass interval between asteroids and brown dwarfs. These event rates are comparable to the frequency of gamma-ray burst detections by the Burst and Transient Source Experiment (BATSE) on the Compton Observatory, implying that if dark halo clusters are the sites of most gamma-ray bursts, perhaps approximately 90% of all bursts are extragalactic, but approximately 10% are galactic. It is possible that dark clusters of the kind discussed here could be detected directly by the Infrared Space Observatory (ISO) or Space Infrared Telescope Facility (SIRTF). If the clusters considered in this paper exist, they should produce spatially correlated gravitational microlensing of stars in the Large Magellanic Cloud (LMC). If 10% of the halo is in the form of dark baryonic clusters, and the remaining 90% is in brown dwarfs and other dark objects which are either unclustered or collected into low-mass clusters, then we expect that two events within approximately 1 min of one another are likely to be seen after a total of order 20-30 microlenses have been detected.

Wasserman, Ira↗

NASA NTRS2023

Using Orbiting Carbon Observatory-2 (OCO-2) column CO2 retrievals to rapidly detect and estimate biospheric surface carbon flux anomalies

The global carbon cycle is experiencing continued perturbations via increases in atmospheric carbon concentrations, which are partly reduced by terrestrial biosphere and ocean carbon uptake. Greenhouse gas satellites have been shown to be useful in retrieving atmospheric carbon concentrations and observing surface and atmospheric CO2 seasonal-to-interannual variations. However, limited attention has been placed on using satellite column CO2 retrievals to evaluate surface CO2 fluxes from the terrestrial biosphere without advanced inversion models at low latency. Such applications could be useful to monitor, in near real time, biosphere carbon fluxes during climatic anomalies like drought, heatwaves, and floods, before more complex terrestrial biosphere model outputs and/or advanced inversion modelling estimates become available. Here, we explore the ability of Orbiting Carbon Observatory-2 (OCO-2) column-averaged dry air CO2 (XCO2) retrievals to directly detect and estimate terrestrial biosphere CO2 flux anomalies using a simple mass-balance approach. An initial global analysis of surface–atmospheric CO2 coupling and transport conditions reveals that the western US, among a handful of other regions, is a feasible candidate for using XCO2 for detecting terrestrial biosphere CO2 flux anomalies. Using the CarbonTracker model reanalysis as a test bed, we first demonstrate that a well-established mass-balance approach can estimate monthly surface CO2 flux anomalies from XCO2 enhancements in the western United States. The method is optimal when the study domain is spatially extensive enough to account for atmospheric mixing and has favorable advection conditions with contributions primarily from one background region. We find that errors in individual soundings reduce the ability of OCO-2 XCO2 to estimate more frequent, smaller surface CO2 flux anomalies. However, we find that OCO-2 XCO2 can often detect and estimate large surface flux anomalies that leave an imprint on the atmospheric CO2 concentration anomalies beyond the retrieval error/uncertainty associated with the observations. OCO-2 can thus be useful for low-latency monitoring of the monthly timing and magnitude of extreme regional terrestrial biosphere carbon anomalies.

Andrew F. Feldman↗

NASA NTRS2021

Exep: Environmental Testing of High-Actuator-Count Mems Deformable Mirrors for Space-Based Applications

Coronagraph instruments on future space telescopes will rely on deformable mirrors to create high contrast images for the direct detection of exoplanets. As part of the NASA Exoplanet Explorations Program’s coronagraph technology development efforts, two sets of Micro-electro-mechanical systems (MEMS) deformable mirrors manufactured by Boston Micromachines Corporation were exposed to vibration and thermal cycles representative of launch conditions. The first set were 952-actuator Kilo-DMs that successfully demonstrated 100% actuator survival and achieved ~1e-8 contrast after the environment test. The second round used an engineering-grade 2048-actuator deformable mirror on which few changes were identified after the environmental test. However, each actuator that changed behavior was flagged as anomalous beforehand or was directly adjacent to a defective actuator. From this result, we hypothesized that typical actuators on a science grade deformable mirror are robust to environmental testing. A third set of 2048-actuator deformable mirror have been procured for a planned test to characterize the deformable mirrors using interferometric measurements, contrast results on a new in-air coronagraph testbed, and infrared microscopy on the internal structure of the MEMS devices.

Lam, Charlie↗

NASA NTRS2002

Profiling Tropospheric Winds with the Goddard Lidar Observatory for Winds (GLOW)

The Goddard Lidar Observatory for Winds (GLOW) is a mobile direct detection Doppler lidar system designed to measure wind profiles from the surface into the lower stratosphere. Recently, the GLOW lidar has participated in several field deployments measuring tropospheric winds in a variety of conditions including both daytime and night operation. More than 50 hours of line-of-sight wind profit data were obtained in September, 2000 during a three week intercomparison experiment at the Ground Winds facility in North Glen, NH. Typical clear air lidar wind profiles extended to altitudes of 20 km with a 1 km vertical resolution and 1 minute averaging. An additional 40 hours of lidar profiles of wind speed and direction were obtained during HARGLO-2, an intercomparison experiment held at Wallops Flight Facility, VA in November, 2001. A description of the mobile system is presented along with the examples of validated lidar wind profiles obtained during these experiments.

Gentry, Bruce M.↗

DOE OSTI2026

Transformative Impacts of Laser-Induced Breakdown Spectroscopy on Environmental and Biological Research at Oak Ridge National Laboratory

This manuscript will present an advancement of transformative research that has been conducted at Oak Ridge National Laboratory (ORNL) over a 25-year period (2000–2025) on a variety of environmental and biological matrices. These investigations derived a fundamental understanding of how elemental detection and analysis of these matrices led to the knowledge and discovery of natural processes in plants and the environment. Each project led to the initiation of a new research area which unearthed awesome and novel breakthroughs. Highlights are listed below: 1. The preliminary research at ORNL centered on the detection of aerosols utilizing Laser-induced Breakdown Spectroscopy (LIBS) technology. The Clean Air Act Amendment (CAAA) of 1990 highlighted the importance of identifying hazardous air pollutants (HAPs) due to their impact on environmental and human health, thereby underscoring the need to detect various toxic elements. Research in aerosol chemistry aimed to identify these harmful elements released by factories during periods of increased emissions in their manufacturing processes. LIBS emerged as the most effective method for real-time, in situ measurements of metal species in both gaseous and aerosol phases. 2. An understanding of the presence of total carbon in soils gives perspective on how to develop carbon sequestration strategies. The recognition that carbon sinks can evolve back to carbon sources to emit back to the atmosphere was an important consideration. Also, the concentration of carbon in soil indicates the health of land areas for growing crops successfully. 3. The direct detection of most of the elements in a wood sample in a single emission spectrum, without sample preparation, encouraged the research to use the LIBS technique for preservative treated wood coupled with use of multivariate statistical methodology. Additionally, it encouraged the researchers to try to differentiate natural woods from different parts of the country, and it was successfully demonstrated that LIBS coupled with MVA analysis could differentiate wood of different species from each other and of similar species grown in different environments based on their elemental spectra. This was a breakthrough since it revealed a systematic approach to connect elemental scarcity and abundance to either drought or typical rainfall conditions for the hardwood trees grown in specific areas. 4. Furthermore, the research progressed to reveal physiological and developmental processes contributing to biomass production such that the variation in leaf elemental composition increases our understanding of terrestrial nutrient cycles, as well as tracking the transfer of toxic elements from soils to living organisms. 5. Recently another breakthrough viz., ionomics initiated the correlation of elements to specific genes, uncovering the function that the element performed in the plant. More recently, this has been extended from plants to fungi as well as fungi growing in symbiotic relations with plants.

09 BIOMASS FUELS↗

NASA NTRS2010

High Velocity Absorption during Eta Car B's Periastron Passage

Eta Car is one of the most luminous massive stars in the Galaxy, with repeated eruptions with a 5.5 year periodicity. These events are caused by the periastron passage of a massive companion in an eccentric orbit. We report the VLT/CRIRES detection of a strong high-velocity, (<1900 km/s) , broad absorption wing in He I at 10833 A during the 2009.0 periastron passage. Previous observations during the 2003.5 event have shown evidence of such high-velocity absorption in the He I 10833 transition, allowing us to conclude that the high-velocity gas is crossing the line-of-sight toward Eta Car over a time period of approximately 2 months. Our analysis of HST/STlS archival data with observations of high velocity absorption in the ultraviolet Si IV and C IV resonance lines, confirm the presence of a high-velocity material during the spectroscopic low state. The observations provide direct detection of high-velocity material flowing from the wind-wind collision zone around the binary system, and we discuss the implications of the presence of high-velocity gas in Eta Car during periastron

Nielsen, Krister E.↗

DOE OSTI2023

In Situ Attenuated Total Reflectance Infrared Spectroelectrochemistry (ATR-IR-SEC) for the Characterization of Molecular Redox Processes on Surface-Proximal Doped Silicon ATR Crystal Working Electrodes

In situ mid-infrared spectroscopy is a powerful technique for understanding the mechanism of CO 2 reduction (CO 2 R) catalysts because it enables the direct detection of catalytic intermediates and products. Moreover, spectroelectrochemistry (SEC), the coupling of spectroscopy with electrochemistry, allows spectroscopic changes to be correlated with applied potentials to reveal potential-dependent intermediates that are often relevant to photoelectrochemical reactions. Hybrid photoelectrodes, comprised of a narrow bandgap semiconductor, like silicon (Si), with a covalently-linked molecular catalyst, are a promising platform for sunlight-driven catalysis, but characterization of the catalytic mechanism(s) is challenging under photoelectrochemical conditions, particularly when the catalyst is present in monolayer or less concentrations. Here, we have developed a new strategy to use multiple-reflection attenuated total reflectance IR spectroscopy (ATR-IR) coupled with electrochemistry to characterize catalysts directly integrated with a semiconductor surface under applied potential. We show that by surface-proximal n-type or p-type doping of the top ~100-200 nm of the crystal surface, Si ATR crystals can be used simultaneously as the internal reflection element and semiconductor working electrode for ATR-IR-SEC measurements. The surface-proximal doping strategy yields a quasi-equipotential surface with excellent infrared transparency that would have been compromised by free carrier absorption if the crystal was uniformly doped. This approach permits the catalytically-active functionalized surface to be directly probed without modification and overcomes signal-to-noise limitations of other strategies that use separately deposited working electrodes on Si ATR crystals. Proof-of-concept ATR-IR-SEC spectra were collected during the reduction and oxidation of monolayers of Re- and Ru-based transition metal carbonyl complexes, respectively, verifying the viability of the technique to probe redox processes associated with CO 2 R catalysts on Si electrode surfaces with high sensitivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2014

Airborne 2-Micron Double-Pulsed Integrated Path Differential Absorption Lidar for Column CO2 Measurement

Double-pulse 2-micron lasers have been demonstrated with energy as high as 600 millijouls and up to 10 Hz repetition rate. The two laser pulses are separated by 200 microseconds and can be tuned and locked separately. Applying double-pulse laser in DIAL system enhances the CO2 measurement capability by increasing the overlap of the sampled volume between the on-line and off-line. To avoid detection complicity, integrated path differential absorption (IPDA) lidar provides higher signal-to-noise ratio measurement compared to conventional range-resolved DIAL. Rather than weak atmospheric scattering returns, IPDA rely on the much stronger hard target returns that is best suited for airborne platforms. In addition, the IPDA technique measures the total integrated column content from the instrument to the hard target but with weighting that can be tuned by the transmitter. Therefore, the transmitter could be tuned to weight the column measurement to the surface for optimum CO2 interaction studies or up to the free troposphere for optimum transport studies. Currently, NASA LaRC is developing and integrating a double-Pulsed 2-micron direct detection IPDA lidar for CO2 column measurement from an airborne platform. The presentation will describe the development of the 2-micron IPDA lidar system and present the airborne measurement of column CO2 and will compare to in-situ measurement for various ground target of different reflectivity.

Singh, Upendra N.↗

DOE OSTI2021

Inelastic dark matter scattering off Thallium cannot save DAMA

We study the compatibility of the observed DAMA modulation signal with inelastic scattering of dark matter (DM) off of the 0.1% Thallium (Tl) dopant in DAMA. In this work we test whether there exist regions of parameter space where the Tl interpretation gives a good fit to the most recent data from DAMA, and whether these regions are compatible with the latest constraints from other direct detection experiments. Previously, Chang et al. in 2010, had proposed the Tl interpretation of the DAMA data, and more recently (in 2019) the DAMA/LIBRA collaboration found regions in parameter space of Tl inelastic scattering that differ by more than 10σ from a no modulation hypothesis. We have expanded upon their work by testing whether the regions of parameter space where inelastic DM-Tl scattering gives a good fit to the most recent DAMA data survive the constraints placed by the lack of a DM signal in XENON1T and CRESST-II. In addition, we have tested how these regions change with the main sources of uncertainty: the Tl quenching factor, which has never been measured directly, and the astrophysical uncertainties in the DM distribution. We conclude that inelastic DM scattering off Tl cannot explain the DAMA data in light of null results from other experiments.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2020

Metastable nuclear isomers as dark matter accelerators

Inelastic dark matter and strongly interacting dark matter are poorly constrained by direct detection experiments since they both require the scattering event to deliver energy from the nucleus into the dark matter in order to have observable effects. We propose to test these scenarios by searching for the collisional deexcitation of metastable nuclear isomers by the dark matter particles. The longevity of these isomers is related to a strong suppression of γ- and β-transitions, typically inhibited by a large difference in the angular momentum for the nuclear transition. The collisional deexcitation by dark matter is possible since heavy dark matter particles can have a momentum exchange with the nucleus comparable to the inverse nuclear size, hence lifting tremendous angular momentum suppression of the nuclear transition. This deexcitation can be observed either by searching for the direct effects of the decaying isomer, or through the rescattering or decay of excited dark matter states in a nearby conventional dark matter detector setup. Existing nuclear isomer sources such as naturally occurring 180m Ta, 137m Ba produced in decaying Cesium in nuclear waste, 177m Lu from medical waste, and 178m Hf from the Department of Energy storage can be combined with current dark matter detector technology to search for this class of dark matter.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2022

Magnetic-Core/Gold-Shell Nanoparticles for the Detection of Hydrophobic Chemical Contaminants

Magnetic-core/gold-shell nanoparticles (MAuNPs) are of interest for enabling rapid and portable detection of trace adulterants in complex media. Gold coating provides biocompatibility and facile functionalization, and a magnetic core affords analyte concentration and controlled deposition onto substrates for surface-enhanced Raman spectroscopy. Iron oxide cores were synthesized and coated with gold by reduction of HAuCl4 by NH2OH. MAuNPs were grafted with polyethylene glycol (PEG) and/or functionalized with 4-mercaptobenzoic acid (4-MBA) and examined using a variety of microscopic, spectroscopic, magnetometric, and scattering techniques. For MAuNPs grafted with both PEG and 4-MBA, the order in which they were grafted impacted not only the graft density of the individual ligands, but also the overall graft density. Significant Raman signal enhancement of the model analyte, 4-MBA, was observed. This enhancement demonstrates the functionality of MAuNPs in direct detection of trace contaminants. The magnetic deposition rate of MAuNPs in chloroform and water was explored. The presence of 4-MBA slowed the mass deposition rate, and it was postulated that the rate disparity originated from differing NP-substrate surface interactions. These findings emphasize the importance of ligand choice in reference to the medium, target analyte, and substrate material, as well as functionalization procedure in the design of similar sensing platforms.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Search for dark matter from the center of the Earth with 10 years of IceCube data

The nature of dark matter remains unresolved in fundamental physics. Weakly Interacting Massive Particles (WIMPs), which could explain the nature of dark matter, can be captured by celestial bodies like the Sun or Earth, leading to enhanced self-annihilation into Standard Model particles including neutrinos detectable by neutrino telescopes such as the IceCube Neutrino Observatory. This article presents a search for muon neutrinos from the center of the Earth performed with 10 years of IceCube data using a track-like event selection. We considered a number of WIMP annihilation channels (χχ→τ+τ-$$\chi \chi \rightarrow \tau ^+\tau ^-$$/W+W-$$W^+W^-$$/bb¯$$b\bar{b}$$) and masses ranging from 10 GeV to 10 TeV. No significant excess over background due to a dark matter signal was found while the most significant result corresponds to the annihilation channel χχ→bb¯$$\chi \chi \rightarrow b\bar{b}$$ for the mass mχ=250$$m_{\chi }=250$$ GeV with a post-trial significance of 1.06σ$$1.06\sigma $$. Our results are competitive with previous such searches and direct detection experiments. Our upper limits on the spin-independent WIMP scattering are world-leading among neutrino telescopes for WIMP masses mχ>100$$m_{\chi }>100$$ GeV.

Abbasi, R↗

DOE OSTI2025

In-Situ FTIR Detection of Transition Metal (TM)-Ion Dissolution From Cathodes in Li-Ion Batteries

Transition metal (TM) ions, commonly Ni and Mn, play a crucial role in Li-ion battery cathodes as the reaction centers for rapid redox reactions. A major challenge with TM-based cathodes is capacity degradation, particularly at higher operating voltages. This degradation is closely linked to the dissolution of TMs from the cathode materials and their subsequent deposition on the anode. This process not only modifies the surface structure of the cathode but, more significantly, alters the SEI composition on the anode [1-2]. The dissolution of TMs cations into a liquid electrolyte from cathode materials, such as Mn-ion dissolution from Mn-rich cathode (LMR), is detrimental to the cycling performance of Li-ion batteries [3-4]. Much attention has been paid to this issue but there remains a lack of characterization techniques which can detect the TM-ion dissolution from the cathode during electrochemical measurements. In our study, we use in-situ ATR-FTIR as an effective technique to probe the TM-ion dissolution from the cathode. We have first demonstrated the detrimental effects of TM ions on the electrochemical performance of Li-ion batteries by adding a small amount of TM salt (50 mM Mn(PF6)) to the electrolyte of a Li-ion coin cell with LFP and graphite electrode. We observed a rapid capacity fade after the first delithiation cycle. To investigate TM ion dissolution, we established a baseline IR spectrum for various TM solvation states (such as Mn and Ni) by measuring concentration-dependent IR spectra. This baseline spectrum helps us detect TM ion dissolution during battery cycling. In this work, we discuss in detail the effect of TM ions on the electrochemical performance of Li-ion batteries and the detection of TM ions during battery cycling using in-situ FTIR spectroscopy. We will compare TM dissolution between coated and uncoated cathodes to examine the effect of cathode coatings to mitigate degradation due to TM dissolution and cross-over from cathode to anode. References: (1) Zhan, C.; Wu, T.; Lu, J.; Amine, K. Dissolution, migration, anddeposition of transition metal ions in Li-ion batteries exemplified byMn-based cathodes - a critical review. Energy Environ. Sci. 2018, 11,243-257. (2) Jung, R.; Linsenmann, F.; Thomas, R.; Wandt, J.; Solchenbach,S.; Maglia, F.; Stinner, C.; Tromp, M.; Gasteiger, H. A. Nickel,Manganese, and Cobalt Dissolution from Ni-Rich NMC and TheirEffects on NMC622-Graphite Cells. J. Electrochem. Soc. 2019, 166,A378-A389. (3) Zhao, L.; Chenard, E.; Capraz, O. O.; Sottos, N. R.; White, S.R. Direct Detection of Manganese Ions in Organic Electrolyte by UV-Vis Spectroscopy. J. Electrochem. Soc. 2018, 165, A345-A348 (4) Zhang, Y.; Hu, A.; Xia, D.; Hwang, S.; Sainio, S.; Nordlund, D.;Michel, F. M.; Moore, R. B.; Li, L.; Lin, F. Operando characterization and regulation of metal dissolution and redeposition dynamics nearbattery electrode surface. Nat. Nanotechnol. 2023, 18, 790.

25 ENERGY STORAGE↗

NASA NTRS1998

Wind Lidar Edge Technique Shuttle Demonstration Mission: Anemos

A NASA mission is planned to demonstrate the technology for a wind lidar. This will implement the direct detection edge technique. The Anemos instrument will fly on the Space Transportation System (STS), or shuttle, aboard a Hitchhiker bridge. The instrument is being managed by the Goddard Space Flight Center as an in-house build, with science leadership from the GSFC Laboratory for Atmospheres, Mesoscale Atmospheric Processes Branch. During a roughly ten-day mission, the instrument will self calibrate and adjust for launch induced mis-alignments, and perform a campaign of measurements of tropospheric winds. The mission is planned for early 2001. The instrument is being developed under the auspices of NASA's New Millennium Program, in parallel with a comparable mission being managed by the Marshall Space Flight Center. That mission, called SPARCLE, will implement the coherent technique. NASA plans to fly the two missions together on the same shuttle flight, to allow synergy of wind measurements and a direct comparison of performance.

Leete, Stephen J.↗

DOE OSTI2021

A New Approach to Fundamental Mechanism Discovery in Polymer Upcycling

We present a new experimental methodology for detailed experimental investigations of depolymerization reactions over solid catalysts. This project aims to address a critical need in fundamental research on chemical upcycling of polymers – the lack of rapid, sensitive, isomerselective probing techniques for the detection of reaction intermediates and products. Our method combines a heterogeneous catalysis reactor for the study of multiphase (gas/polymer melt/solid) systems, coupled to a vacuum UV photoionization time-of-flight mass spectrometer. This apparatus draws on our expertise in probing complex gas-phase chemistry and enables highthroughput, detailed chemical speciation measurements of the gas phase above the catalyst, providing valuable information on the heterogeneous catalytic reactions. Using this approach, we investigated the depolymerization of high-density polyethylene (HDPE) over Ir-doped zeolite catalysts. We showed that the product distribution was dominated by low-molecular weight alkenes with terminal C=C double bonds and revealed the presence of many methyl-substituted alkenes and alkanes, suggesting extensive methyl radical chemistry. In addition, we investigated the fundamental reactivity of model oligomer molecules n-butane and isobutane over ZSM-5 zeolites. We demonstrated the first direct detection of methyl radical intermediates, confirming the key role of methyl in zeolite-catalyzed activation of alkanes. Our results show the potential of this experimental method to achieve deep insight into the complex depolymerization reactions and pave the way for detailed mechanistic studies, leading to increased fundamental understanding of key processes in chemical upcycling of polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRSDate not supplied

Constraining Venus Cloud Habitability: Earth's Aerobiosphere as an Analogue Environment

The potential habitability of Venus's cloud and haze layers has been debated for decades, with interest fueled by observations including disequilibria in atmospheric chemistry, strongly UV-absorbing particles, and (most recently) a controversial phosphine detection. Venus cloud temperature and pressure are clement by Earth standards; however, the calculated high acid activity and low water activity may exceed the limits of Earth biochemistry, based on observed life in extreme environments. A significant challenge in understanding Venus's habitability is the lack of an appropriate terrestrial analogue environment. Life has not been found in hydrothermal systems approaching Venus aerosol acidities, but these systems also contain high levels of other harsh solutes. Earth's stratospheric sulfate layer is a partial match in terms of acidity, desiccation, size, and isolation from the surface, but the few samples returned from these altitudes have yielded only sparse, inactive cells. Earth's tropospheric cloud droplets have an active microbial presence, but are larger and far more water-rich than Venus aerosols; tropospheric times aloft are also similar to microbial generation times, making Earth's aerobiosphere dependent on continuous surface replenishment. Direct detection of potential biosignatures from a single transect is challenging; Earth's cloud microbiota yields 102 - 108 viable cells per mL, equivalent to one per 103 - 109 particles, with highly dynamic and heterogeneous distribution. The most important in situ measurement for Venus cloud habitability is detailed aerosol composition: confirmation of acid and water activity, presence of potentially bioavailable nutrients and energy, and potential presence of organic matter. Modeling Venus cloud aerosol residence time in comparison to periodic influxes of water and photochemical energy, and thus the ability of an ecosystem to maintain itself over time, would also address a significant habitability constraint particular to aerobiospheres.

Venus↗