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Kinetics, Products, and Brown Carbon Formation by Aqueous-Phase Reactions of Glycolaldehyde with Atmospheric Amines and Ammonium Sulfate

Glycolaldehyde (GAld) is a C 2 water-soluble aldehyde produced during the atmospheric oxidation of isoprene and many other species and is commonly found in cloudwater. Previous work has established that glycolaldehyde evaporates more readily from drying aerosol droplets containing ammonium sulfate (AS) than does glyoxal, methylglyoxal, or hydroxyacetone, which implies that it does not oligomerize as quickly as these other species. Here, we report NMR measurements of glycolaldehyde’s aqueous-phase reactions with AS, methylamine, and glycine. Reaction rate constants are smaller than those of respective glyoxal and methylglyoxal reactions in the pH range of 3–6. In follow-up cloud chamber experiments, deliquesced glycine and AS seed particles were found to take up glycolaldehyde and methylamine and form brown carbon. At very high relative humidity, these changes were more than 2 orders of magnitude faster than predicted by our bulk liquid NMR kinetics measurements, suggesting that reactions involving surface-active species at crowded air–water interfaces may play an important role. The high-resolution liquid chromatography–electrospray ionization–mass spectrometric analysis of filter extracts of unprocessed AS + GAld seed particles identified sugar-like C 6 and C 12 GAld oligomers, including proposed product 3-deoxyglucosone, with and without modification by reactions with ammonia to diimine and imidazole forms. Chamber exposure to methylamine gas, cloud processing, and simulated sunlight increased the incorporation of both ammonia and methylamine into oligomers. Many C 4 –C 16 imidazole derivatives were detected in an extract of chamber-exposed aerosol along with a predominance of N-derivatized C 6 and C 12 glycolaldehyde oligomers, suggesting that GAld is capable of forming brown carbon SOA.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced Far Ultra-Violet Optical Properties of Physical Vapor Deposited Aluminum Mirrors Through Fluorination

Astronomical instrumentation for measurements in the Far Ultra-Violet (FUV, 90-200 nm) typically use aluminum (Al) thin films due to their high reflectance over this wavelength range. However, the native aluminum oxide layer that forms on Al upon exposure to the atmosphere is strongly absorbing in this wavelength range, requiring that the films be protected with a dielectric that inhibits oxidation. Typically, magnesium fluoride (MgF 2 ) or lithium fluoride (LiF) coatings are used as protective layers, but each has shortcomings. For example, MgF 2 has an absorption cutoff at 115 nm reducing performance in a critical part of the FUV spectrum of observational interest. A viable option to access these lower wavelengths could be the use of the LiF overcoat as it has a lower absorption cutoff at 102.5 nm, but it is hygroscopic and thus susceptible to degradation in humid conditions. An approach to reduce the hygroscopic nature of LiF would be to implement a passivation process during the deposition of both Al+LiF coatings. Our team at GSFC has developed a new reactive Physical Vapor Deposition (rPVD) process that consists of a fluorination process with XeF 2 gas combined with our traditional PVD process. We have found that this new rPVD coating process offers a protected version of Al+LiF with a more environmentally stable and more transparent LiF layer, along with unprecedent reflectivity. The process starts with a bare optically smooth substrate that is coated with Al in an ultra-high vacuum (UHV) chamber by the conventional PVD process. Then, the bare Al mirror is immediately exposed to a reactive XeF 2 gas before and after the application of the flash PVD evaporated LiF layer. We have also been investigating the use of this rPVD coating process for potential efficiency enhancements of Si-based gratings. Since it is known that the XeF 2 vapor is a strong Si etchant, we are investigating if the native SiO 2 layer on Si is sufficient to protect the groove profile of e-beam-ruled Si gratings from degradation. We will report on the characterization of various Al+LiF witness mirror coatings (both on borosilicate and Si) performed under various deposition conditions using the XeF 2 passivation process. These tests include XPS to determine film stoichiometry and AFM/SEM to measure surface roughness and any etching on the Si substrate. We will also report on FUV reflectance and spectroscopic ellipsometry to characterize optical constants of these passivated films in the UV/Visible/NIR spectral ranges.

Engineering (General)↗

Enhanced Far Ultra-Violet Optical Properties of Physical Vapor Deposited Aluminum Mirrors Through Fluorination

Astronomical instrumentation for measurements in the Far Ultra-Violet (FUV, 90-200 nm) typically use aluminum (Al) thin films due to their high reflectance over this wavelength range. However, the native aluminum oxide layer that forms on Al upon exposure to the atmosphere is strongly absorbing in this wavelength range, requiring that the films be protected with a dielectric that inhibits oxidation. Typically, magnesium fluoride (MgF 2 ) or lithium fluoride (LiF) coatings are used as protective layers, but each has shortcomings. For example, MgF 2 has an absorption cutoff at 115 nm reducing performance in a critical part of the FUV spectrum of observational interest. A viable option to access these lower wavelengths could be the use of the LiF overcoat as it has a lower absorption cutoff at 102.5 nm, but it is hygroscopic and thus susceptible to degradation in humid conditions. An approach to reduce the hygroscopic nature of LiF would be to implement a passivation process during the deposition of both Al+LiF coatings. Our team at GSFC has developed a new reactive Physical Vapor Deposition (rPVD) process that consists of a fluorination process with XeF 2 gas combined with our traditional PVD process. We have found that this new rPVD coating process offers a protected version of Al+LiF with a more environmentally stable and more transparent LiF layer, along with unprecedent reflectivity. The process starts with a bare optically smooth substrate that is coated with Al in an ultra-high vacuum (UHV) chamber by the conventional PVD process. Then, the bare Al mirror is immediately exposed to a reactive XeF 2 gas before and after the application of the flash PVD evaporated LiF layer. We have also been investigating the use of this rPVD coating process for potential efficiency enhancements of Si-based gratings. Since it is known that the XeF 2 vapor is a strong Si etchant, we are investigating if the native SiO 2 layer on Si is sufficient to protect the groove profile of e-beam-ruled Si gratings from degradation. We will report on the characterization of various Al+LiF witness mirror coatings (both on borosilicate and Si) performed under various deposition conditions using the XeF 2 passivation process. These tests include XPS to determine film stoichiometry and AFM/SEM to measure surface roughness and any etching on the Si substrate. We will also report on FUV reflectance and spectroscopic ellipsometry to characterize optical constants of these passivated films in the UV/Visible/NIR spectral ranges.

Engineering (General)↗

Enhanced Far Ultra-Violet Optical Properties of Physical Vapor Deposited Aluminum Mirrors Through Fluorination

Astronomical instrumentation for measurements in the Far Ultra-Violet (FUV, 90-200 nm) typically use aluminum (Al) thin films due to their high reflectance over this wavelength range. However, the native aluminum oxide layer that forms on Al upon exposure to the atmosphere is strongly absorbing in this wavelength range, requiring that the films be protected with a dielectric that inhibits oxidation. Typically, magnesium fluoride (MgF 2 ) or lithium fluoride (LiF) coatings are used as protective layers, but each has shortcomings. For example, MgF 2 has an absorption cutoff at 115 nm reducing performance in a critical part of the FUV spectrum of observational interest. A viable option to access these lower wavelengths could be the use of the LiF overcoat as it has a lower absorption cutoff at 102.5 nm, but it is hygroscopic and thus susceptible to degradation in humid conditions. An approach to reduce the hygroscopic nature of LiF would be to implement a passivation process during the deposition of both Al+LiF coatings. Our team at GSFC has developed a new reactive Physical Vapor Deposition (rPVD) process that consists of a fluorination process with XeF 2 gas combined with our traditional PVD process. We have found that this new rPVD coating process offers a protected version of Al+LiF with a more environmentally stable and more transparent LiF layer, along with unprecedent reflectivity. The process starts with a bare optically smooth substrate that is coated with Al in an ultra-high vacuum (UHV) chamber by the conventional PVD process. Then, the bare Al mirror is immediately exposed to a reactive XeF 2 gas before and after the application of the flash PVD evaporated LiF layer. We have also been investigating the use of this rPVD coating process for potential efficiency enhancements of Si-based gratings. Since it is known that the XeF 2 vapor is a strong Si etchant, we are investigating if the native SiO 2 layer on Si is sufficient to protect the groove profile of e-beam-ruled Si gratings from degradation. We will report on the characterization of various Al+LiF witness mirror coatings (both on borosilicate and Si) performed under various deposition conditions using the XeF 2 passivation process. These tests include XPS to determine film stoichiometry and AFM/SEM to measure surface roughness and any etching on the Si substrate. We will also report on FUV reflectance and spectroscopic ellipsometry to characterize optical constants of these passivated films in the UV/Visible/NIR spectral ranges.

Engineering (General)↗

Habitability Assessments And Lessons-learned From 3-day And 11-day Enriched Oxygen Hypobaric Chamber Tests At NASA Johnson Space Center

INTRODUCTION: Decompression sickness (DCS) is a risk to the health and performance of astronauts and high-altitude aircrew. Tolerance to flammability, hypoxia, prebreathe duration, and DCS risk varies across different organizations, vehicles, suits, and destinations, necessitating a variety of DCS risk mitigation approaches. Existing models of altitude DCS risk are often insufficient to enable accurate risk-informed decisions during hardware development, mission planning, and flight operations. METHODS: NASA completed outfitting of a dedicated facility at Johnson Space Center to support testing of up to eight human subjects for multiple days in hypobaric and enriched oxygen atmospheres. The primary purpose of the testing capability is validation of DCS risk mitigation protocols for Artemis missions to the Moon; however, it will also support development and validation of a generalizable altitude DCS risk estimation tool. A 3-day and an 11-day prebreathe validation test were completed in 2022, each with 8 human subjects living at 56.5 kPa (8.2 psia), 34% O2, 66% N2, with 5 simulated EVAs performed on masks at 29.6 kPa (4.3 psi), 85% O2, 15% N2. Facility and organizational lessons-learned and process improvements were recorded during and following the tests, and subjective habitability ratings were recorded daily during the 11-day test. Hypoxia and DCS-related physiological and cognitive outcome measures were recorded during both tests and are reported in companion presentations. RESULTS & DISCUSSION: All subjects completed each of the tests. Primary habitability issues related to mask discomfort during simulated EVAs and poor sleep quality due to thin mattresses. Polybenzimidazole (PBI) clothing was worn by all subjects due to the increased fire risk and may be required for Artemis missions; clothing was found to be acceptable overall with the worst ratings being due to poor fit and inelasticity. Chamber O2 and CO2 sensor inconsistency was observed that did not result in test termination but required post-test follow-up. Forward plans include additional hypobaric testing and integration of existing and future physiological outcome data into an open-source Aerospace Estimation Tool for Hypobaric Exposure Risk (AETHER). NASA is also working to make the testing capability available to commercial companies.

Andrew F J Abercromby↗

Habitability Assessments And Lessons-learned From 3-day And 11-day Enriched Oxygen Hypobaric Chamber Tests At NASA Johnson Space Center

INTRODUCTION: Decompression sickness (DCS) is a risk to the health and performance of astronauts and high-altitude aircrew. Tolerance to flammability, hypoxia, prebreathe duration, and DCS risk varies across different organizations, vehicles, suits, and destinations, necessitating a variety of DCS risk mitigation approaches. Existing models of altitude DCS risk are often insufficient to enable accurate risk-informed decisions during hardware development, mission planning, and flight operations. METHODS: NASA completed outfitting of a dedicated facility at Johnson Space Center to support testing of up to eight human subjects for multiple days in hypobaric and enriched oxygen atmospheres. The primary purpose of the testing capability is validation of DCS risk mitigation protocols for Artemis missions to the Moon; however, it will also support development and validation of a generalizable altitude DCS risk estimation tool. A 3-day and an 11-day prebreathe validation test were completed in 2022, each with 8 human subjects living at 56.5 kPa (8.2 psia), 34% O2, 66% N2, with 5 simulated EVAs performed on masks at 29.6 kPa (4.3 psi), 85% O2, 15% N2. Facility and organizational lessons-learned and process improvements were recorded during and following the tests, and subjective habitability ratings were recorded daily during the 11-day test. Hypoxia and DCS-related physiological and cognitive outcome measures were recorded during both tests and are reported in companion presentations. RESULTS & DISCUSSION: All subjects completed each of the tests. Primary habitability issues related to mask discomfort during simulated EVAs and poor sleep quality due to thin mattresses. Polybenzimidazole (PBI) clothing was worn by all subjects due to the increased fire risk and may be required for Artemis missions; clothing was found to be acceptable overall with the worst ratings being due to poor fit and inelasticity. Chamber O2 and CO2 sensor inconsistency was observed that did not result in test termination but required post-test follow-up. Forward plans include additional hypobaric testing and integration of existing and future physiological outcome data into an open-source Aerospace Estimation Tool for Hypobaric Exposure Risk (AETHER). NASA is also working to make the testing capability available to commercial companies.

Andrew Abercromby↗

Survival of endospores of Bacillus subtilis on spacecraft surfaces under simulated martian environments: implications for the forward contamination of Mars

Experiments were conducted in a Mars simulation chamber (MSC) to characterize the survival of endospores of Bacillus subtilis under high UV irradiation and simulated martian conditions. The MSC was used to create Mars surface environments in which pressure (8.5 mb), temperature (-80, -40, -10, or +23 degrees C), gas composition (Earth-normal N2/O2 mix, pure N2, pure CO2, or a Mars gas mix), and UV-VIS-NIR fluence rates (200-1200 nm) were maintained within tight limits. The Mars gas mix was composed of CO2 (95.3%), N2 (2.7%), Ar (1.7%), O2 (0.2%), and water vapor (0.03%). Experiments were conducted to measure the effects of pressure, gas composition, and temperature alone or in combination with Mars-normal UV-VIS-NIR light environments. Endospores of B. subtilis, were deposited on aluminum coupons as monolayers in which the average density applied to coupons was 2.47 x 10(6) bacteria per sample. Populations of B. subtilis placed on aluminum coupons and subjected to an Earth-normal temperature (23 degrees C), pressure (1013 mb), and gas mix (normal N2/O2 ratio) but illuminated with a Mars-normal UV-VIS-NIR spectrum were reduced by over 99.9% after 30 sec exposure to Mars-normal UV fluence rates. However, it required at least 15 min of Mars-normal UV exposure to reduce bacterial populations on aluminum coupons to non-recoverable levels. These results were duplicated when bacteria were exposed to Mars-normal environments of temperature (-10 degrees C), pressure (8.5 mb), gas composition (pure CO2), and UV fluence rates. In other experiments, results indicated that the gas composition of the atmosphere and the temperature of the bacterial monolayers at the time of Mars UV exposure had no effects on the survival of bacterial endospores. But Mars-normal pressures (8.5 mb) were found to reduce survival by approximately 20-35% compared to Earth-normal pressures (1013 mb). The primary implications of these results are (a) that greater than 99.9% of bacterial populations on sun-exposed surfaces of spacecraft are likely to be inactivated within a few tens of seconds to a few minutes on the surface of Mars, and (b) that within a single Mars day under clear-sky conditions bacterial populations on sun-exposed surfaces of spacecraft will be sterilized. Furthermore, these results suggest that the high UV fluence rates on the martian surface can be an important resource in minimizing the forward contamination of Mars. c2003 Elsevier Inc. All rights reserved.

Bacillus subtilis/growth & development/physiology/↗

Sample Materials Considerations for Curating and Processing Pristine MSR Samples

The perseverance rover is collecting and caching samples of Mars as part of the Mars 2020 mission, which represents the first leg of a multi-mission Mars Sample Return Campaign. The MSR Campaign is an international partnership that will result in delivery of the first martian samples to Earth that were not delivered through meteoritic infall. All meteorites, regardless of how they were handled from recovery to curation, have experienced uncontrolled entry and exposure to the terrestrial environment. Whilst meteorite deliveries are serendipitous, they are also unplanned events that require reactionary responses for recovery and curation. However, with the direct return of pristine astromaterials from another body, we are afforded the ability to design a facility in advance of sample delivery to keep those samples in a pristine (i.e., as returned) state for an indefinite period of time. Given that the curation and processing infrastructure needs to be made out of something, it is important to choose materials for the pristine curation environment that will optimize between the need to effectively process samples and the need to minimize contamination of the samples. The Johnson Space Center (JSC) has an optimized list of materials that have been used in previous sample return missions that includes 304/316 Stainless Steel, Teflon, and T6061 Aluminum (1). This set of materials are compatible with inorganic, organic, and biological cleanliness requirements and protocols. Furthermore, only these materials are permitted to come in contact with pristine samples. We note that JSC uses Neoprene and Hypalon for the gloves on their gloveboxes, but the glove material never comes in direct contact with the samples, only the approved materials. The MSR sample tubes will be made of Ti, so Ti may be an acceptable material for making tools, but the minor and trace element abundances of 304 and 316 stainless steel are well known and do not inhibit scientific investigations of metals, including HSE (2). More work is needed to determine whether the same is true for Ti alloys. In addition to defining the materials in the pristine environment, one must also choose whether the pristine environment will be under vacuum or under a specific atmospheric composition and pressure. Although JAXA has successfully implemented pristine curation vacuum chambers for their Hayabusa and Hayabusa2 samples (3), a vacuum environment is not appropriate for martian samples because it may drive deliquescence of mineral phases in the samples that are sensitive to pressure and relative humidity (4). Consequently, the pristine environment for the martian samples should be under an inert gas. It will be crucial to minimize the number of gases that come into direct contact with samples and these gases will need to be high purity and consistent throughout the pristine isolators. Samples at JSC are stored under high purity gaseous nitrogen (1). Dry N2 gas has not been a problem for N isotope studies for high-T release phases, but an additional inert atmosphere like Ar may be needed for samples where there is a particular concern about low-T release of N from bulk sample analysis. References: (1) McCubbin FM, et al. (2019) Space Science Reviews, 215, 1-81. (2) Day JMD, et al. (2018) Meteorit. Planet. Sci. 53:1283-1291. (3) Yada, T., et al., (2014). Meteorit. Planet. Sci. 49, 135-153. (4) Tosca NJ, et al. (2021). Astrobiology, in press, doi:10.1089/ast.2021.0115.

F M McCubbin↗

The effect of repeated altitude exposures on the incidence of decompression sickness

INTRODUCTION: Repeated altitude exposures in a single day occur during special operations parachute training, hypobaric chamber training, unpressurized flight, and extravehicular space activity. Inconsistent and contradictory information exists regarding the risk of decompression sickness (DCS) during such hypobaric exposures. HYPOTHESIS: We hypothesized that four short exposures to altitude with and without ground intervals would result in a lower incidence of DCS than a single exposure of equal duration. METHODS: The 32 subjects were exposed to 3 different hypobaric exposures--condition A: 2 h continuous exposure (control); condition B: four 30-min exposures with descent/ascent but no ground interval between the exposures; condition C: four 30-min exposures with descent/ascent and 60 min of ground interval breathing air between exposures. All exposures were to 25,000 ft with 100% oxygen breathing. Subjects were observed for symptoms of DCS, and precordial monitoring of venous gas emboli (VGE) was accomplished with a SONOS 1000 echo-imaging system. RESULTS: DCS occurred in 19 subjects during A (mean onset 70+/-29 min), 7 subjects in B (60+/-34 min), and 2 subjects in C (40+/-18 min). There was a significant difference in DCS incidence between B and A (p = 0.0015) and C and A (p = 0.0002), but no significant difference between B and C. There were 28 cases of VGE in A (mean onset 30+/-23 min), 21 in B (41+/-35 min), and 21 in C (41+/-32 min) with a significant onset curve difference between B and A and between C and A, but not between B and C. Exposure A resulted in four cases of serious respiratory/neurological symptoms, while B had one and C had none. All symptoms resolved during recompression to ground level. CONCLUSION: Data indicate that repeated simulated altitude exposures to 25,000 ft significantly reduce DCS and VGE incidence compared with a single continuous altitude exposure.

Non-NASA Center↗

Engineering the Interface: Advanced Surface Technologies for Lunar Dust Management and Equipment Longevity

Through the Artemis program, NASA intends to develop a sustainable human foothold on the Moon, ultimately paving the way for crewed exploration of Mars. The Moon's hostile environment poses numerous obstacles, including exposure to radiation, temperature extremes, micrometeoroid threats, and particularly the persistent problem of lunar dust. Lunar dust impacts nearly every aspect of surface operations through adhesion and abrasion mechanisms, with contamination from anthropogenic activities (landing, rovers) far outweighing natural phenomena. Multiple adhesion pathways contribute to surface contamination in the lunar environment, including van der Waals forces, electrostatic forces, chemical reaction, and magnetic forces from elemental iron deposits. Sharp asperities from micrometeoroid bombardment and atmospheric absence increase interaction potential and enable mechanical interlocking. Low cohesion between dust particles exacerbates these challenges, as minimal interaction potential between dust and nearby surfaces overcomes particle cohesion, causing contamination. Lunar dust adhesion mitigation technologies can be categorized as either active, requiring external energy, or passive, relying on intrinsic material properties. Ultrasonic and electrodynamic technologies have been developed to the highest technology readiness level for active approaches. Passive strategies primarily focus on surface chemistry and topography modifications. At NASA Langley Research Center, approaches include surface migration agents to reduce surface energy, topographical modification using laser ablation patterning, and tailored surface conductivity to reduce intrinsic adhesion force. Performance has been evaluated using custom-built ultrasonic and centrifuge instruments. Plume-surface interactions from lunar landers can propel micrometer-sized particles at velocities up to 1000 m s-1.8 These particles pose risks to landers, habitats and infrastructure, leading to erosion, degradation, and reduced component lifespan. A panel recovered from Surveyor III was determined to have been severely abraded because of lunar dust displaced from the Apollo 12 lunar module that landed 160 m away. The performance of metallic surfaces has been evaluated via high velocity single particle impact using the laser-induced project impact test (LIPIT) facility at the University of Utah. Peridynamics modeling, a form of continuum mechanics that uses a nonlocal approach enabling greater simulation capabilities of crack initiation and fracture, has also been utilized to gain greater insight into material response during impact events. Lunar dust contamination challenges extend to power generation systems and moving equipment. Cables, rotation stages, and other mechanisms may experience limited range of motion and reduced lifetime due to dust infiltration. NASA Langley Research Center has evaluated traditional aerospace alloys, softgoods, wear resistant ceramics, and several polymer and polymer composite materials. Test methods have included traditional techniques like Taber abrasion testing, as well as designed test configurations developed in the DUSTE (dust, ultraviolet radiation, and space thermal environmental) chamber that reproduce mechanism functions in operational environment. Beyond laboratory experiments, several flight experiments have been conducted. Materials were exposed to the low Earth orbit environment on the Materials International Space Station Experiment (MISSE) and to the lunar surface environment through the Aegis Aerospace Regolith Adherence Characterization (RAC) payload and the Honeybee Robotics PlanetVac payload. Determining lunar dust's impact on surface exploration and habitation requires comprehensive experimental and computational capabilities combined with lessons learned from initial lunar activities. Identifying the greatest environmental challenges and developing mitigation technologies provides the clearest path toward successfully, expeditiously, and efficaciously completing NASA's mission. This presentation will discuss ongoing efforts at NASA Langley Research Center and collaborator contributions to these critical objectives.

Surface Engineering↗