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NASA NTRS2021

Volatile Organic Compounds Emitted from Air Fresheners: Plug-Ins at Home and Little Trees in Cars

Air fresheners contain volatile organic compounds (VOCs), some of which are possible hazardous air pollutants, carcinogens, or chemicals associated with adverse health effects such as asthma. This screening study identifies VOCs emitted from two types of air fresheners. Plug-in air fresheners are household products that release scents from a heated liquid. Little Tree air fresheners are commonly used solid devices designed to hang in from the rear view mirror in cars. VOCs that were released from heated samples of air fresheners were identified by gas chromatography mass spectroscopy (GCMS). Amongst VOCs commonly known to have scent properties, this screening also revealed the presence of compounds that are not associated with fragrances and that may have adverse health effects. In a pilot study to characterize how air fresheners affect air quality in real settings, air samples were collected on solid-phase microextraction (SPME) field samplers in a home setting and inside a vehicle, before and during air-freshener use. This pilot demonstrated some limited potential for SPME field samplers to track changes in VOC levels in real-life settings.

Adriana Pino-Delgado↗
NASA NTRS2009

Oxygen Production from Lunar Regolith using Ionic Liquids

The objective of this work and future follow-on work is to develop a safe, efficient, and recyclable method for oxygen and/or metals extraction from lunar regolith, in support of establishing a manned lunar outpost. The approach is to solubilize the oxides that comprise lunar regolith in media consisting of ionic liquids (ILs) and/or their mixtures at temperatures at or below 300 C. Once in solution, electrolysis can either be performed in-situ to generate oxygen at the anode and hydrogen and/or metals (silicon, iron, aluminum, titanium, etc.) at the cathode. Alternatively, the water that is generated during the solubilization process can be distilled out and condensed into a separate IL and then electrolysized to produce hydrogen and oxygen. In the case of lunar regolith, this method could theoretically produce 44g oxygen per 100g of regolith. The oxygen can be used for human life support and/or as an oxidizer for rocket fuels, and the metals can be used as raw materials for construction and/or device fabrication. Moreover, the hydrogen produced can be used to re-generate the acidic medium, which can then be used to process additional regolith, thereby making the materials recyclable and limiting upmass requirements. An important advantage of IL acid systems is that they are much "greener" and safer than conventional materials used for regolith processing such as sulfuric or hydrochloric acids. They have very low vapor pressures, which means that they contain virtually no toxic and/or flammable volatile content, they are relatively non-corrosive, and they can exhibit good stability in harsh environments (extreme temperatures, hard vacuum, etc.). Furthermore, regolith processing can be achieved at lower temperatures than other processes such as molten oxide electrolysis or hydrogen reduction, thereby reducing initial power requirements. Six ILs have been synthesized and tested for their capability to dissolve lunar simulant, and for electrochemical and thermal stability. The results showed that ILs can be very efficient electrolytes; in particular IL/phosphoric-acid mixtures appear extremely promising for solubilizing lunar simulant. Results from preliminary experiments for distillation of water produced from the oxygen within the metal oxides of the simulant and the hydrogen from the acid indicates that over 75% of the oxygen from the simulant can be harvested as water at a temperature of 150 C. A method for collection of oxygen from electrolysis of the water derived from solubilizing simulant was developed by using a liquid nitrogen trap to liquefy and collect the oxygen. Although precise quantification of the liquid oxygen trapped is difficult to obtain, the amount of hydrogen and oxygen collected from electrolysis of water in this system was greater than 98%. This set-up also included a portable mass spectrometer for the identification of gases released from electrolysis cells. Regeneration of ILs through re-protonation was also demonstrated. Four sequential re-generations of an IL following solubilization of simulant showed no significant differences in amounts of simulant dissolved. Follow-on work for this project should include more studies of IL/phosphoric acid systems. Also, much more work is necessary for defining methods for electrolysis and purification of metals from regolith solubilized in ILs, and for developing a system to use the produced hydrogen to regenerate the spent IL. Finally, design and development of flight breadboard and prototype hardware is required.

Paley, Mark Steven↗
NASA NTRS2013

NASA Technology Evaluation for Environmental Risk Mitigation Remediation Technology Collaboration Development

NASA is committed to finding solutions to agency cleanup problems that are better, cheaper, and more effective than the status quo. Unfortunately, some potential solutions involve innovative technologies for which NASA remediation managers may not have a high level of understanding or confidence. Since 2004, NASA's Stennis Space Center (SSC) in Mississippi has been pumping groundwater contaminated with trichloroethylene (TCE) and other halogenated volatile organic compounds (HVOC) from their cleanup location designated "Area G" through extraction wells to an aboveground treatment system. Over time, however, the effectiveness of this treatment strategy has diminished and an alternative approach is needed. In 2012, professionals from NASA's Principal Center for Technology Evaluation for Environmental Risk Mitigation (TEERM) introduced SSC managers to an innovative technology for enhancing the performance of SSC's existing pump and treat system. The technology, generally referred to as in situ chemical oxidation (ISCO), involves slowly and continuously injecting a strong but safe chemical oxidant into the groundwater. Treatment is enhanced by a "surfactant-type effect" which causes residual contamination from saturated soil to be released into the dissolved-phase where it can be readily oxidized. Any dissolved-phase contamination that was not oxidized can be collected by the extraction well network and treated aboveground. SSC was not familiar with the technology so to increase their confidence, TEERM identified a contractor who was willing to demonstrate their product and process at a significantly reduced price. An initial, small-scale demonstration of ISCO began at sse in March 2012 and completed in August 2012. This successful demonstration was followed by three larger-scale ISCO demonstrations between August and December 2012. The contractor's innovative Continuous Injection System (CIS) incorporated "green" and sustainable technologies and practices. A slow injection rate was maintained autonomously by the CIS, eliminating the need for multiple mobilizations of personnel and powered equipment. The CIS was calibrated to deliver only as much reagent as the formation would accept without "short circuiting", minimizing material waste. Public utility water pressure was used to mix, dilute, and inject the reagent. NASA personnel were trained to operate and maintain the system and remote monitoring and injection control capabilities were developed, further reducing the need for contractor mobilizations to the site. An integrated solar photovoltaic panel was used to power the control valves and web monitoring telemetry. SSC provided hydrogen peroxide for the process using their existing supplier for the aboveground pump and treat systems. The only consumable required from the contractor was their proprietary activator to catalyze SSC's peroxide.

Romeo, James↗
NASA NTRS2000

Regolith Evolved Gas Analyzer

The Regolith Evolved Gas Analyzer (REGA) is a high-temperature furnace and mass spectrometer instrument for determining the mineralogical composition and reactivity of soil samples. REGA provides key mineralogical and reactivity data that is needed to understand the soil chemistry of an asteroid, which then aids in determining in-situ which materials should be selected for return to earth. REGA is capable of conducting a number of direct soil measurements that are unique to this instrument. These experimental measurements include: (1) Mass spectrum analysis of evolved gases from soil samples as they are heated from ambient temperature to 900 C; and (2) Identification of liberated chemicals, e.g., water, oxygen, sulfur, chlorine, and fluorine. REGA would be placed on the surface of a near earth asteroid. It is an autonomous instrument that is controlled from earth but does the analysis of regolith materials automatically. The REGA instrument consists of four primary components: (1) a flight-proven mass spectrometer, (2) a high-temperature furnace, (3) a soil handling system, and (4) a microcontroller. An external arm containing a scoop or drill gathers regolith samples. A sample is placed in the inlet orifice where the finest-grained particles are sifted into a metering volume and subsequently moved into a crucible. A movable arm then places the crucible in the furnace. The furnace is closed, thereby sealing the inner volume to collect the evolved gases for analysis. Owing to the very low g forces on an asteroid compared to Mars or the moon, the sample must be moved from inlet to crucible by mechanical means rather than by gravity. As the soil sample is heated through a programmed pattern, the gases evolved at each temperature are passed through a transfer tube to the mass spectrometer for analysis and identification. Return data from the instrument will lead to new insights and discoveries including: (1) Identification of the molecular masses of all of the gases liberated from heated soil samples; (2) Identification of the asteroid soil mineralogy to aid in the selection process for returned samples; (3) Existence of oxygen in the asteroid soil and the potential for in-situ resource utilization (ISRU); and (4) Existence of water and other volatiles in the asteroid soil. Additional information is contained in the original extended abstract.

Hoffman, John H.↗
NASA NTRSDate not supplied

Comparing Analysis of Hydrogen Concentration in Astromaterials Nominally Anhydrous Minerals by Multiple SIMS

Secondary Ion Mass Spectrometry (SIMS) is utilized to determine hydrogen (H) concentration in astromaterials nominally anhydrous minerals (NAMs) and their inclusions [e.g., 1]. This data is interpreted to refine the volatile history of planetary bodies. Four instruments are being used to compare H concentration analysis: a large geometry SIMS (The University of Hawaiʻi Cameca IMS 1280), a compact SIMS (Arizona State University (ASU) Cameca IMS 6f), and two Cameca NanoSIMS 50L at ASU and NASA-Johnson Space Center (JSC). Results on the first three instruments are available. Although fundamentally similar, SIMS instruments and their modifications [2] may produce different values or pose advantages for H analysis, especially for shocked samples that are susceptible to contamination filling their fractures. New data from the IMS 1280 is reported, using its microchannel plate (MCP) to image high H signals in grain fractures during pre-sputtering to avoid them as much as possible. Between fractures, 16 OH/ 30 Si was measured with a Cs + 4 nA primary beam, 30 micron spot size, and central ~5x5 micron collection area. First order comparison of H concentration (reported in ppm H 2 O) is achieved on a terrestrial gem quality clinopyroxene (SLP114, 162±12 ppm H 2 O [3]), with 157±7 and 215±40 ppm H 2 O by the IMS 1280 and 6f respectively. SIMS comparison is then extended to analysis of two Martian shergottites: RBT 04262 and NWA 5789. Due to a dense fracture network (< 20 micron) in RBT 04262, only one clinopyroxene hosted glassy inclusion was analyzed (n=6, ≤1 ppm H 2 O), while six olivine grains in NWA 5789 (n=12, ≤ 2 ppm H 2 O) (1s ±0.21) were analyzed. Higher concentrations were obtained for RBT 04262 olivine by the ASU NanoSIMS 50L (up to 350 ppm H 2 O [4]), and IMS 6f (300+ ppm H 2 O, [5]), for which contamination in fractures could not be avoided. Work on the JSC NanoSIMS 50L will further develop the SIMS comparison.

J.-M. Dudley↗
NASA NTRS2014

Lunar Flashlight: Mapping Lunar Surface Volatiles Using a Cubesat

Water ice and other volatiles may be located in the Moon's polar regions, with sufficient quantities for in situ extraction and utilization by future human and robotic missions. Evidence from orbiting spacecraft and the LCROSS impactor suggests the presence of surface and/or nearsurface volatiles, including water ice. These deposits are of interest to human exploration to understand their potential for use by astronauts. Understanding the composition, quantity, distribution, and form of water/H species and other volatiles associated with lunar cold traps is identified as a NASA Strategic Knowledge Gap (SKG) for Human Exploration. These polar volatile deposits could also reveal important information about the delivery of water to the Earth- Moon system, so are of scientific interest. The scientific exploration of the lunar polar regions was one of the key recommendations of the Planetary Science Decadal Survey. In order to address NASA's SKGs, the Advanced Exploration Systems (AES) program selected three lowcost 6-U CubeSat missions for launch as secondary payloads on the first test flight (EM1) of the Space Launch System (SLS) scheduled for 2017. The Lunar Flashlight mission was selected as one of these missions, specifically to address the SKG associated with lunar volatiles. Development of the Lunar Flashlight CubeSat concept leverages JPL's Interplanetary Nano- Spacecraft Pathfinder In Relevant Environment (INSPIRE) mission, MSFC's intimate knowledge of the Space Launch System and EM-1 mission, small business development of solar sail and electric propulsion hardware, and JPL experience with specialized miniature sensors. The goal of Lunar Flashlight is to determine the presence or absence of exposed water ice and its physical state, and map its concentration at the kilometer scale within the permanently shadowed regions of the lunar south pole. After being ejected in cislunar space by SLS, Lunar Flashlight deploys its solar panels and solar sail and maneuvers into a low-energy transfer to lunar orbit. The solar sail and attitude control system work to bring the satellite into an elliptical polar orbit spiraling down to a perilune of 30-10 km above the south pole for data collection. Lunar Flashlight uses its solar sail to shine reflected sunlight into permanently shadowed regions, measuring surface albedo with a four-filter point spectrometer at 1.1, 1.5 1.9, and 2.0 microns. Water ice will be distinguished from dry regolith from these measurements in two ways: 1) spatial variations in absolute reflectance (water ice is much brighter in the continuum channels), and 2) reflectance ratios between absorption and continuum channels. Derived reflectance and reflectance ratios will be mapped onto the lunar surface in order to distinguish the composition of the PSRs from that of the sunlit terrain. Lunar Flashlight enables a low-cost path to in-situ resource utilization (ISRU) by identifying operationally useful deposits (if there are any), which is a game-changing capability for expanded human exploration.

Cohen, B. A.↗
NASA NTRS2009

Quick-Connect Windowed Non-Stick Penetrator Tips for Rapid Sampling

Standard penetrator sampling systems were designed in order to allow for sampling via penetrators to produce a full set of sample acquisitions including volatile liquids, fine powders, and solid fragments. A gravity harpoon sampler has been designed with a removable tip and a quick coupling. The separation allows for sample handling and eliminates sample cross-contamination. Also, this design allows for multiple use of the penetrator body, which is the largest and heaviest part of the penetrator, while allowing for multiple changes of the light-mass, penetrator tip to avoid sample cross-contamination. The penetrator tip design has been improved by adding a spring trap to retain the sample, as well as a means for connecting to a quick coupling. Quick connect tips have been demonstrated in a sample handling carousel. The penetrator was released and rewound and the tips were released into a circular platter for rotation into instrument stations. The pyro-harpoon sampler was fabricated and tested with a NASA Standard Initiator (NSI) pyrotechnic charge. Initial tests collected cryogenic ice, but removal of the small pyro-harpoon from the ice was difficult. A brass metal sheath was then fitted over the harpoon tip, and removal from the ice was greatly alleviated by leaving the sheath in the ice. Quartz windows in the tips allow direct optical and spectral imaging and gas chromatography-mass spectrometer (GCMS) pyrolysis, and were found to survive impact. All systems were successfully tested by dropping into sand and into cryogenic ice.

Sherritt, Stewart↗
NASA NTRS2022

Changes in Anthropogenic Precursor Emissions Drive Shifts in the Ozone Seasonal Cycle Throughout the Northern Midlatitude Troposphere

Simulations by six Coupled Model Intercomparison Project Phase 6 (CMIP6) Earth system models indicate that the seasonal cycle of baseline tropospheric ozone at northern midlatitudes has been shifting since the mid-20th century. Beginning in ∼ 1940, the magnitude of the seasonal cycle increased by ∼10 ppb (measured from seasonal minimum to maximum), and the seasonal maximum shifted to later in the year by about 3 weeks. This shift maximized in the mid-1980s, followed by a reversal – the seasonal cycle decreased in amplitude and the maximum shifted back to earlier in the year. Similar changes are seen in measurements collected from the 1970s to the present. The timing of the seasonal cycle changes is generally concurrent with the rise and fall of anthropogenic emissions that followed industrialization and the subsequent implementation of air quality emission controls. A quantitative comparison of the temporal changes in the ozone seasonal cycle at sites in both Europe and North America with the temporal changes in ozone precursor emissions across the northern midlatitudes found a high degree of similarity between these two temporal patterns. We hypothesize that changing precursor emissions are responsible for the shift in the ozone seasonal cycle; this is supported by the absence of such seasonal shifts in southern midlatitudes where anthropogenic emissions are much smaller. We also suggest a mechanism by which changing emissions drive the changing seasonal cycle: increasing emissions of NOx allow summertime photochemical production of ozone to become more important than ozone transported from the stratosphere, and increasing volatile organic compounds (VOCs) lead to progressively greater photochemical ozone production in the summer months, thereby increasing the amplitude of the seasonal ozone cycle. Decreasing emissions of both precursor classes then reverse these changes. The quantitative parameter values that characterize the seasonal shifts provide useful benchmarks for evaluating model simulations, both against observations and between models.

Ozone↗
NASA NTRS1993

Extraction and isotopic analysis of medium molecular weight hydrocarbons from Murchison using supercritical carbon dioxide

The large variety of organic compounds present in carbonaceous chondrites poses particular problems in their analysis not the least of which is terrestrial contamination. Conventional analytical approaches employ simple chromatographic techniques to fractionate the extractable compounds into broad classes of similar chemical structure. However, the use of organic solvents and their subsequent removal by evaporation results in the depletion or loss of semi-volatile compounds as well as requiring considerable preparative work to assure solvent purity. Supercritical fluids have been shown to provide a powerful alternative to conventional liquid organic solvents used for analytical extractions. A sample of Murchison from the Field Museum was analyzed. Two interior fragments were used; the first (2.85 g) was crushed in an agate pestel and mortar to a grain size of ca. 50-100 micron, the second (1.80 g) was broken into chips 3-8 mm in size. Each sample was loaded into a stainless steel bomb and placed in the extraction chamber of an Isco supercritical fluid extractor maintained at 35 C. High purity (99.9995 percent) carbon dioxide was used and was pressurized using an Isco syringe pump. The samples were extracted dynamically by flowing CO2 under pressure through the bomb and venting via a 50 micron fused filica capillary into 5 mls of hexane used as a collection solvent. The hexane was maintained at a temperature of 0.5 C. A series of extractions were done on each sample using CO2 of increasing density. The principal components extracted in each fraction are summarized.

Gilmour, Iain↗
NASA NTRS2011

NASA Lunabotics Mining Competition for Universities: Results and Lessons Learned

Space Mining for resources such as water ice, and regolith, which contain many elements in the form of metals, minerals, volatiles and other compounds, is a necessary step in Space Resource Utilization. One of the primary goals is to extract propellants from the regolith such as oxygen and hydrogen which could then be used for in-space transportation. In addition, the space mining system can be used for various construction tasks that can benefit human and robotic exploration as well as scientific investigations based on the exposed topography. The National Aeronautics & Space Administration (NASA) Lunabotics Mining Competition is a university-level competition designed to engage and retain students in science, technology, engineering and mathematics (STEM). NASA will directly benefit from the competition by encouraging the development of innovative lunar excavation concepts from universities which may result in clever ideas and solutions which could be applied to an actual lunar excavation device or payload. The challenge is for students to design and build a remote controlled or autonomous excavator, called a lunabot, that can collect and deposit a minimum of 10 kilograms of lunar simulant within 15 minutes. The complexities of the challenge include the abrasive characteristics of the lunar simulant, the weight and size limitations of the lunabot, and the ability to control the lunabot from a remote control center. This paper will present the results of the first and second annual Lunabotics Mining Competitions held in May 2010 and May 2011. In 2010, 22 United States (US) universities competed, and in May 2011 the competition was opened to international participation, with 46 Universities expected to attend. There are 12 international teams and 34 US teams. This combined total directly inspired an estimated 544 university students. More students and the public were engaged via internet broadcasting and social networking media. The various designs will be cataloged and categorized to provide information to future Lunabotics mining robot designers and competitors. It is also expected to be of value for actual future space missions, as knowledge is gained from testing many innovative prototypes in simulated lunar regolith.

Mueller, Robert P.↗
NASA NTRS2012

Lunabotics Mining Competition: Inspiration through Accomplishment

Space Mining for resources such as water ice, and regolith, which contain many elements in the form of metals, minerals, volatiles and other compounds, is a necessary step in Space Resource Utilization. One of the primary goals is to extract propellants from the regolith such as oxygen and hydrogen which could then be used for in-space transportation. In addition, the space mining system can be used for various construction tasks that can benefit human and robotic exploration as well as scientific investigations based on the exposed topography. The National Aeronautics & Space Administration (NASA) Lunabotics Mining Competition is a university-level competition designed to engage and retain students in science, technology, engineering and mathematics (STEM). NASA will directly benefit from the competition by encouraging the development of innovative lunar excavation concepts from universities which may result in clever ideas and solutions which could be applied to an actual lunar excavation device or payload. The challenge is for students to design and build a remote controlled or autonomous excavator, called a lunabot, that can collect and deposit a minimum of 10 kilograms of lunar simulant within 15 minutes. The complexities of the challenge include the abrasive characteristics of the lunar simulant, the weight and size limitations of the lunabot, and the ability to control the lunabot from a remote control center or operate autonomously. This paper will present an update of the results and lessons learned during the first and second annual Lunabotics Mining Competitions held in May 2010 and May 2011. It will also preview the 2012 competition with a review of the revised rules. In 2010,22 United States (US) universities competed, and in May 2011 the competition was opened to international participation. In 2011, 36 teams actually competed from 26 USA states and 4 foreign countries (India, Bangladesh, Colombia and Canada). This combined total directly inspired an estimated 653 university students. In 2012 more students and the public will be engaged via internet broadcasting and social networking media. The various designs will be cataloged and categorized to provide information to future Lunabotics mining robot designers and competitors. It is also expected to be of value for actual future space missions, as knowledge is gained from testing many innovative prototypes in simulated lunar regolith.

Mueller, Robert P.↗
NASA NTRS1982

Methane and nonmethane hydrocarbon concentrations in the North and South Atlantic marine boundary layer

Methane and nonmethane hydrocarbon (NMHC) data were collected in the Atlantic marine boundary layer from 40 N to 32 S latitude during October and November 1980. Average volume mixing ratios for CH4 of 1.69 + or - 0.02 ppmv were obtained north of the intertropical convergence zone (ITCZ) and 1.60 + or - 0.02 ppmv south of the ITCZ. The hemispheric CH4 gradient was very sharp, decreasing rapidly between 14 N and 10 N latitude. Gaseous NMHC concentrations (based on response as CH4) were measured simultaneously and found to lie consistently within the standard error for the individual measurements + or - 0.02 ppmv) after correction for water vapor interference. The correction for water vapor response was large, frequently as much as 80% of the raw NMHC signal. Application of the student's t distribution test to the NMHC data set established that the mean northern and southern hemispheric NMHC mixing ratios measured, 0.016 and 0.010 ppmv, respectively, were statistically different at the 95% confidence level. These results indicate volatile NMHC mixing ratios average less than 0.02 ppmv over the Atlantic and represent the first set of semicontinuous NMHC measurements spanning the North and South Atlantic marine boundary layer.

Cofer, W. R., III↗
NASA NTRS2014

SAM-Like Evolved Gas Analyses of Phyllosilicate Minerals and Applications to SAM Analyses of the Sheepbed Mudstone, Gale Crater, Mars

While in Yellowknife Bay, the Mars Science Laboratory Curiosity rover collected two drilled samples, John Klein (hereafter "JK") and Cumberland ("CB"), from the Sheepbed mudstone, as well as a scooped sample from the Rocknest aeolian bedform ("RN"). These samples were sieved by Curiosity's sample processing system and then several subsamples of these materials were delivered to the Sample Analysis at Mars (SAM) instrument suite and the CheMin X-ray diffraction/X-ray fluorescence instrument. CheMin provided the first in situ X-ray diffraction-based evidence of clay minerals on Mars, which are likely trioctahedral smectites (e.g., Fe-saponite) and comprise ~20 wt% of the mudstone samples [1]. SAM's evolved gas analysis (EGA) mass spectrometry analyses of JK and CB subsamples, as well as RN subsamples, detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, OCS, CS2 and other trace gases evolved during pyrolysis. The identity of evolved gases and temperature( s) of evolution can augment mineral detection by CheMin and place constraints on trace volatile-bearing phases present below the CheMin detection limit or those phases difficult to characterize with XRD (e.g., X-ray amorphous phases). Here we will focus on the SAM H2O data, in the context of CheMin analyses, and comparisons to laboratory SAM-like analyses of several phyllosilicate minerals including smectites.

McAdam, A. C.↗
NASA NTRS2016

Production of Peroxy Nitrates in Boreal Biomass Burning Plumes over Canada During the BORTAS Campaign

The observations collected during the BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites (BORTAS) campaign in summer 2011 over Canada are analysed to study the impact of forest fire emissions on the formation of ozone (O3 and total peroxy nitrates (sigma)PNs, (sigma)ROONO2. The suite of measurements on board the BAe-146 aircraft, deployed in this campaign, allows us to calculate the production of O3 and of (sigma)PNs, a long-lived NOx reservoir whose concentration is supposed to be impacted by biomass burning emissions.In fire plumes, profiles of carbon monoxide (CO), which is a well-established tracer of pyrogenic emission, show concentration enhancements that are in strong correspondence with a significant increase of concentrations of (sigma)PNs, where as minimal increase of the concentrations of O3 and NO2 is observed. The (sigma)PN and O3 productions have been calculated using the rate constants of the first- and second-order react Pions of volatile organic compound (VOC) oxidation. The (sigma)PN and O3 productions have also been quantified by 0-D model simulation based on the Master Chemical Mechanism. Both methods show that in fire plumes the average production of (sigma)PNs and O3 are greater than in the background plumes, but the increase of (sigma)PN production is more pronounced than the O3 production. The average (sigma)PN production in fire plumes is from 7 to 12 times greater than in the background, whereas the average O3 production in fire plumes is from 2 to 5 times greater than in the background. These results suggest that, at least for boreal forest fires and for the measurements recorded during the BORTAS campaign,fire emissions impact both the oxidized NOy and O3;but (1)(sigma)PN production is amplified significantly more thanO3 production and (2) in the forest fire plumes the ratio between the O3 production and the (sigma)PN production is lower than the ratio evaluated in the background air masses, thus confirming that the role played by the (sigma)PNs produced during biomass burning is significant in the O3 budget. The implication of these observations is that fire emissions in some cases, for example boreal forest fires and in the conditions reported here, may influence more long-lived precursors of O3than short-lived pollutants, which in turn can be transported and eventually diluted in a wide area.

biomass burning↗
NASA NTRS2004

Analysis of the Atmospheric Distribution, Sources, and Sinks of Oxygenated Volatile Organic Chemicals Based on Measurements over the Pacific during TRACE-P

Airborne measurements of a large number of oxygenated volatile organic chemicals (OVOC) were carried out in the Pacific troposphere (0.1-12 km) in winter/spring of 2001 (24 February to 10 April). Specifically, these measurements included acetone (CH3COCH3), methylethyl ketone (CH3COC2H5, MEK), methanol (CH3OH), ethanol (C2H5OH), acetaldehyde (CH3CHO), propionaldehyde (C2H5CHO), peroxyacylnitrates (PANs) (C(sub n)H(sub 2n+1)COO2NO2), and organic nitrates (C(sub n)H(sub 2n+1)ONO2). Complementary measurements of formaldehyde (HCHO), methyl hydroperoxide (CH3OOH), and selected tracers were also available. OVOC were abundant in the clean troposphere and were greatly enhanced in the outflow regions from Asia. Background mixing ratios were typically highest in the lower troposphere and declined toward the upper troposphere and the lowermost stratosphere. Their total abundance (Summation of OVOC) was nearly twice that of nonmethane hydrocarbons (Summation of C2-C8 NMHC). Throughout the troposphere, the OH reactivity of OVOC is comparable to that of methane and far exceeds that of NMHC. A comparison of these data with western Pacific observations collected some 7 years earlier (February-March 1994) did not reveal significant differences. Mixing ratios of OVOC were strongly correlated with each other as well as with tracers of fossil and biomass/biofuel combustion. Analysis of the relative enhancement of selected OVOC with respect to CH3Cl and CO in 12 plumes originating from fires and sampled in the free troposphere (3-11 km) is used to assess their primary and secondary emissions from biomass combustion. The composition of these plumes also indicates a large shift of reactive nitrogen into the PAN reservoir thereby limiting ozone formation. A three-dimensional global model that uses state of the art chemistry and source information is used to compare measured and simulated mixing ratios of selected OVOC. While there is reasonable agreement in many cases, measured aldehyde concentrations are significantly larger than predicted. At their observed levels, acetaldehyde mixing ratios are shown to be an important source of HCHO (and HO x ) and PAN in the troposphere. On the basis of presently known chemistry, measured mixing ratios of aldehydes and PANs are mutually incompatible. We provide rough estimates of the global sources of several OVOC and conclude that collectively these are extremely large (150-500 Tg C / yr) but remain poorly quantified.

Singh, H. B.↗
NASA NTRS2012

Siderophile Element Constraints on the Conditions of Core Formation in Mars

Siderophile element concentrations in planetary basalts and mantle samples have been used to estimate conditions of core formation for many years and have included applications to Earth, Moon, Mars and asteroid 4 Vesta [1]. For Earth, we have samples of mantle and a diverse collection of mantle melts which have provided a mature understanding of the how to reconstruct the concentration of siderophile elements in mantle materials, from only concentrations in surficial basalt (e.g., [2]). This approach has led to the consensus views that Earth underwent an early magma ocean stage to pressures of 40-50 GPa (e.g., [3,4]), Moon melted extensively and formed a small (approx. 2 mass %) metallic core [5], and 4 Vesta contains a metallic core that is approximately 18 mass % [6,7]. Based on new data from newly found meteorites, robotic spacecraft, and experimental partitioning studies, [8] showed that eight siderophile elements (Ni, Co, Mo, W, Ga, P, V and Cr) are consistent with equilibration of a 20 mass% S-rich metallic core with the mantle at pressures of 14 +/- 3 GPa. We aim to test this rather simple scenario with additional analyses of meteorites for a wide range of siderophile elements, and application of new experimental data for the volatile siderophile and highly siderophile elements.

Righter, K.↗
NASA NTRS2017

Development and Testing of Harpoon-Based Approaches for Collecting Comet Samples

Comets, having bright tails visible to the unassisted human eye, are considered to have been known about since pre-historic times. In fact 3,000-year old written records of comet sightings have been identified. In comparison, asteroids, being so dim that telescopes are required for observation, were not discovered until 1801. Yet, despite their later discovery, a space mission returned the first samples of an asteroid in 2010 and two more asteroid sample return missions have already been launched. By contrast no comet sample return mission has ever been funded, despite the fact that comets in certain ways are far more scientifically interesting than asteroids. Why is this? The basic answer is the greater difficulty, and consequently higher cost, of a comet sample return mission. Comets typically are in highly elliptical heliocentric orbits which require much more time and propulsion for Space Craft (SC) to reach from Earth and then return to Earth as compared to many asteroids which are in Earth-like orbits. It is also harder for a SC to maneuver safely near a comet given the generally longer communications distances and the challenge of navigating in the comet's, when the comet is close to perihelion, which turns out to be one of the most interesting times for a SC to get close to the comet surface. Due to the science value of better understanding the sublimation of volatiles near the comet surface, other contributions to higher cost as desire to get sample material from both the comet surface and a little below, to preserve the stratigraphy of the sample, and to return the sample in a storage state where it does not undergo undesirable alterations, such as aqueous. In response to these challenges of comet sample return missions, the NASA Goddard Space Flight Center (GFSC) has worked for about a decade (2006 to this time) to develop and test approaches for comet sample return that would enable such a mission to be scientifically valuable, while having acceptably low risk and an affordable cost. A harpoon-based approach for gathering comet samples appears to offer the most effective way of accomplishing this goal. As described below, with a decade of development, analysis, testing and refinement, the harpoon approach has evolved from a promising concept to a practical element of a realistic comet sample return mission. Note that the following material includes references to videos, all of which are contained in different sections of the video supplement identified in the references. Each video will be identified as "SS##", where "SS" means the supplement section and "##" will be the number of the section.

Purves, Lloyd↗
NASA NTRS2024

Xenon Isotopic Analysis of Individual Intermediate Particles From the OSIRIS-REx Sample of Asteroid Bennu

The OSIRIS-REx mission sampled material from the B-type asteroid Bennu and delivered the sample to Earth on 24 September 2023. Here we present initial xenon isotopic analysis of individual intermediate particles of Bennu material collected by the OSIRIS-REx mission. Noble gases are key tracers of Solar System evolution. Xenon is particularly useful among the noble gases because its nine isotopes allow multiple contributing sources to be unambiguously identified. The sun, asteroids (as measured in meteorites), and comets (measured in the coma of comet 67P) have distinct xenon isotopic signatures reflecting different mixtures of nucleosynthetic components. In addition, 129 I, 238 U, and 244 Pu decay with different half-lives, producing characteristic xenon signatures. Exposure of samples containing light rare earth elements and barium to cosmic rays produces xenon from spallation and secondary neutron capture reaction. Noble gas analyses help address several of the driving hypotheses of the mission [9]. Particle-by-particle analysis can elucidate the diversity of material present and reveal distinct noble gas compositions, including the potential to detect presolar or cometary noble gas signatures on a small scale. The isotopic signature provides a fingerprint that can be used to constrain the sources of volatiles in planetary reservoirs and combined with other information (e.g. mineralogy and petrology of the material analyses) contributes to our understanding of the initial constituents, formation, and history of Bennu and its parent asteroid.

S A Crowther↗