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At least 127 records · Page 7

Volatile products from the interaction of KCl(g) with Cr2O3 and LaCrO3 in oxidizing environments

Cooled target collection techniques and high pressure mass spectrometric sampling were used to measure the relative rates of oxidative vaporization and to identify the volatile products emanating from samples of chromia and Mg-doped lanthanum chromite. The materials were exposed to partial pressures of KCl with and without H2O in one atmosphere of slowly flowing oxygen at elevated temperatures. Chromia and fresh samples of lanthanum chromite exhibited enhanced rates of oxidative vaporization upon exposure to these reactants. Mass spectrometric identification showed that the enhancements resulted from the heterogeneous formation of complex molecules of the type KCl sub 1,2,3 CrO3 and KOH sub l,2 CrO3. Lanthanum chromite that had undergone prolonged oxidative vaporization exhibited no enhanced oxidation upon exposure to the reactants.

Kohl, F. J.↗

Demonstration of an Automated System for Vertical Profiles of Volatile Organic Compounds

Volatile organic compounds (VOCs) play important roles throughout the atmosphere, many of which are altitude dependent. This highlights the need for easily deployable devices to sample VOCs across different atmospheric layers. To address this, we present the design and initial application of a Time Resolved Automated Volatile organIc compounds Sampling system (TRAVIS). VOCs are collected on sorbent tubes, which are subsequently analyzed by a thermal desorption gas chromatography mass spectrometry pipeline. TRAVIS leverages a piezoelectric pump with an integrated pressure sensor for precise (0.1% flow rate relative standard deviation) and accurate (−3 ± 2% error in VOC quantitation) measurements. Via deployment on a tethered balloon system over an agricultural area, TRAVIS is used to show consistent vertically resolved VOC concentrations in a well-mixed (i.e., turbulent) atmosphere (e.g., 5% relative standard deviation for isoprene) and vertically dependent concentrations for a stratified atmosphere (e.g., prior to boundary layer development). Furthermore, we also show VOC information from an intermittent plume via both targeted and untargeted analysis, highlighting future applications for spurious events in agriculture, air quality monitoring, and environmental impact. Overall, the development of TRAVIS represents a lightweight, accurate, sensitive, and precise VOC sampling module for the scientific community.

Aerosols↗

Chemical changes in thirdhand smoke associated with remediation using an ozone generator

Ozonation is a common remediation approach to eliminate odors from mold, tobacco and fire damage in buildings. Little information exists to: 1) assess its effectiveness; 2) provide guidance on operation conditions; and 3) identify potential risks associated with the presence of indoor ozone and ozonation byproducts. The goal of this study is to evaluate chemical changes in thirdhand smoke (THS) aerosols induced by high levels of ozone, in comparison with THS aerosols aged under similar conditions in the absence of ozone. Samples representing different stages of smoke aging in the absence of ozone, including freshly emitted secondhand smoke (SHS) and THS, were collected inside an 18-m 3 room-sized chamber over a period of 42 h after six cigarettes were consumed. The experiments involved collection and analysis of gas phase species including volatile organic compounds (VOCs), volatile carbonyls, semivolatile organic compounds (SVOCs), and particulate matter. VOC analysis was carried out by gas chromatography/mass spectrometry with a thermal desorption inlet (TD-GC/MS), and volatile carbonyls were analyzed by on-line derivatization with dinitrophenylhydrazine (DNPH), followed by liquid chromatography with UV/VIS detection. SVOCs were extracted from XAD-coated denuders and Teflon-coated fiberglass filters in the absence of ozone. In those extracts, tobacco-specific nitrosamines (TSNAs) and other SVOCs were analyzed by gas chromatography with positive chemical ionization-triple quadrupole mass spectrometric detection (GC/PCI-QQQ-MS), and polycyclic aromatic hydrocarbons (PAHs) were quantified by gas chromatography with ion trap mass spectrometric detection (GC/IT-MS) in selected ion monitoring mode. Particulate matter concentration was determined gravimetrically. In a second experiment, a 300 mg h -1 commercial ozone generator was operated during 1 h, one day after smoke was generated, to evaluate the remediation of THS by ozonation. VOCs and volatile carbonyls were analyzed before and after ozonation. Extracts from fabrics that were exposed in the chamber before and after ozonation as surrogates for indoor furnishings were analyzed by GC/IT-MS, and aerosol size distribution was studied with a scanning mobility particle sizer. Ozone concentration was measured with a photometric detector. An estimated 175 mg ozone reacted with THS after 1 h of treatment, corresponding to 58% of the total O 3 released during that period. Fabric-bound nicotine was depleted after ozonation, and the surface concentration of PAHs adsorbed to fabric specimens decreased by an order of magnitude due to reaction with ozone, reaching pre-smoking levels. These results suggest that ozonation has the potential to remove harmful THS chemicals from indoor surfaces. However, gas phase concentrations of volatile carbonyls, including formaldehyde, acetaldehyde and acetone were higher immediately after ozonation. Ultrafine particles (UFP, in most cases with size <60 nm) were a major ozonation byproduct. UFP number concentrations peaked shortly after ozonation ended, and remained at higher-than background levels for several hours. Based on these results, minimum re-entry times after ozone treatment were predicted for different indoor scenarios. Clearly defining re-entry times can serve as a practical measure to prevent acute exposures to ozone and harmful ozonation byproducts after treatment. This study evaluated potential benefits and risks associated with THS remediation using ozone, providing insights into this technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Oxygen isotope evidence from Ryugu samples for early water delivery to Earth by CI chondrites

The delivery of water to the inner Solar System, including Earth, is still a debated topic. A preferential role for hydrated asteroids in this process is supported by isotopic measurements. Carbonaceous chondrite (CC) meteorites represent our main source of information about these volatile-rich asteroids. However, the destruction of weaker materials during atmospheric entry creates a bias in our CC data. The return of surface materials from the C-type asteroid 162173 Ryugu by the Hayabusa2 spacecraft provides a unique opportunity to study high-porosity, low-density, primitive materials, unrepresented in the meteorite record. We measured the bulk oxygen isotope composition from four Ryugu particles and show that they most closely resemble the rare CI (CC Ivuna-type) chondrites, but with some differences that we attribute to the terrestrial contamination of the CI meteorites. We suggest that CI-related material is widespread among carbonaceous asteroids and a more important source of Earth’s water and other volatiles than its limited presence in our meteoritic collection indicates.

58 GEOSCIENCES↗

Exobiology science objectives at a lunar base

Five general categories of experimentation on the moon are reviewed which would provide important scientific information about chemical evolution and the origin and early evolution of life. Attention is given to: (1) chemical analyses of samples for products of prebiotic evolution, (2) analysis of crater records and understanding the implications for the origin and evolution of life on earth, (3) exposure of microbes and organics to the space environment, (4) collection of cosmic dust particles and analysis of volatiles and organics, and (5) observations of planetary environments and the interstellar medium to determine the nature and extent of chemical evolution.

Devincenzi, Donald L.↗

Field demonstration of DNAPL dehalogenation using emulsified zero-valent iron

This paper describes the results of the first field-scale demonstration conducted to evaluate the performance of nanoscale emulsified zero-valent iron (EZVI) injected into the saturated zone to enhance in situ dehalogenation of dense, nonaqueous phase liquids (DNAPLs) containing trichloroethene (TCE). EZVI is an innovative and emerging remediation technology. EZVI is a surfactant-stabilized, biodegradable emulsion that forms emulsion droplets consisting of an oil-liquid membrane surrounding zero-valent iron (ZVI) particles in water. EZVI was injected over a five day period into eight wells in a demonstration test area within a larger DNAPL source area at NASA's Launch Complex 34 (LC34) using a pressure pulse injection method. Soil and groundwater samples were collected before and after treatment and analyzed for volatile organic compounds (VOCs) to evaluate the changes in VOC mass, concentration and mass flux. Significant reductions in TCE soil concentrations (>80%) were observed at four of the six soil sampling locations within 90 days of EZVI injection. Somewhat lower reductions were observed at the other two soil sampling locations where visual observations suggest that most of the EZVI migrated up above the target treatment depth. Significant reductions in TCE groundwater concentrations (57 to 100%) were observed at all depths targeted with EZVI. Groundwater samples from the treatment area also showed significant increases in the concentrations of cis-1,2-dichloroethene (cDCE), vinyl chloride (VC) and ethene. The decrease in concentrations of TCE in soil and groundwater samples following treatment with EZVI is believed to be due to abiotic degradation associated with the ZVI as well as biodegradation enhanced by the presence of the oil and surfactant in the EZVI emulsion.

Water Pollutants/isolation & purification↗

Results from the Gas Chromatograph Mass Spectrometer (GCMS) Experiment on the Cassini-Huygens Probe

The GCMS was part of the instrument complement on the Cassini-Huygens Probe to measure in situ the chemical composition of the atmosphere during the probe descent and coupled with the Aerosol Collector Pyrolyser (ACP) experiment by serving as detector for the pyrolization products to determine the composition of the aerosol particles. The GCMS employed a quadrupole mass filter with a secondary electron multiplier detection system and a gas sampling system providing continuous direct atmospheric composition measurements and batch sampling through three gas chromatographic (GC) columns, a chemical scrubber and a hydrocarbon enrichment cell. The GCMS gas inlet was heated to prevent condensation, and to evaporate volatiles from the surface after impact. The GCMS collected data from an altitude of 146 km to ground impact. The Probe and the GCMS survived impact and collected data for 1 hour and 9 minutes on the surface. Mass spectra were collected during descent and on the ground over a range of m/z from 2 to 141. The major constituents of the lower atmosphere were confirmed to be NP and CH4. The methane mole fraction was uniform in the stratosphere. It increased below the tropopause, at about 32 km altitude, monotonically toward the surface, reaching a plateau at about 8 km at a level near saturation. After surface impact a steep increase of the methane signal was observed, suggesting evaporation of surface condensed methane due to heating by the GCMS sample inlet heater. The measured mole fraction of Ar-40 is 4.3 x 10(exp-5) and of Ar-36 is 2.8 x 10(exp -7). The other primordial noble gases were below mole fraction. The isotope ratios of C-12/C-13 determined from methane measurements are 82.3 and of N-14/N-15 determined from molecular nitrogen are 183. The D/H isotope ratio determined from the H2 and HD measurements is 2.3 x l0(exp -4). Carbon dioxide, ethane, acetylene and cyanogen were detected evaporating from the surface in addition to methane.

Niemann, Hasso B.↗

Field Demonstration of DNAPL Dehalogenation Using Emulsified Zero-Valent Iron

This paper describes the results of the first field-scale demonstration conducted to evaluate the performance of nano-scale emulsified zero-valent iron (EZVI) injected into the saturated zone to enhance in situ dehalogenation of dense, non-aqueous phase liquids (DNAPLs) containing trichloroethene (TCE). EZVI is an innovative and emerging remediation technology. EZVI is a surfactant-stabilized, biodegradable emulsion that forms emulsion droplets consisting of an oil-liquid membrane surrounding zero-valent iron (ZVI) particles in water. EZVI was injected over a five day period into eight wells in a demonstration test area within a larger DNAPL source area at NASA's Launch Complex 34 (LC34) using a pressure pulse injection method. Soil and groundwater samples were collected before and after treatment and analyzed for volatile organic compounds (V005) to evaluate the changes in VOC mass, concentration and mass flux. Significant reductions in TCE soil concentrations (>80%) were observed at four of the six soil sampling locations within 90 days of EZVI injection. Somewhat lower reductions were observed at the other two soil sampling locations where visual observations suggest that most of the EZVI migrated up above the target treatment depth. Significant reductions in TCE groundwater concentrations (57 to 100%) were observed at all depths targeted with EZVI. Groundwater samples from the treatment area also showed significant increases in the concentrations of cis-1,2-dichloroethene (cDCE), vinyl chloride (VC) and ethene. The decrease in concentrations of TCE in soil and groundwater samples following treatment with EZVI is believed to be due to abiotic degradation associated with the ZVI as well as biodegradation enhanced by the presence of the oil and surfactant in the EZVI emulsion.

Quinn, Jacqueline↗

BOREAS TGB-10 Volatile Organic Carbon Data over the SSA

The BOREAS TGB-10 team collected several trace gas data sets in its efforts to determine the role of biogenic hydrocarbon emissions with respect to boreal forest carbon cycles. This data set contains measured VOC concentrations. These data were obtained at the SSA-OJP site from May to September 1994. The data are stored in tabular ASCII files.

Westberg, Hal↗

The development of a volatile organics concentrator for use in monitoring Space Station water quality

A breadboard concept of a volatile organics concentrator (VOC) is manufactured and tested for optimized water-quality analysis in a space environment. The VOC system is attached to a gas chromatograph/mass spectrometer to analyze the volatile chemicals relevant to the operation of Space Station Freedom. The preliminary tests include: (1) comparisons with analyses based on direct on-column injections of standards; (2) analyses of iodinated volatile organics; (3) comparisons of nitrogen vs helium as the chromatography carrier gas; and (4) measurements of collection efficiency. The VOC can analyze EPA method-624 analytes at comparable detection using flame-ionization detection and can analyze volatile iodinated compounds. The breadboard has good reproducibility and can use nitrogen as a carrier gas; good results are noted for the collection and concentration levels and for water removal.

Bodek, Itamar↗

Un-Numbered Operational Areas PRL 229 Railroad Tie Disposal Area Pond Confirmation Sampling Report

This Confirmatory Sampling (CS) Report (CSR) was prepared for the National Aeronautics and Space Administration (NASA), Kennedy Space Center (KSC), Florida in accordance with the CS Work Plan (CSWP) (HGL, 2022a). The CSR summarizes investigation activities performed on the Railroad Tie Disposal Area (RTDA) of the Un-Numbered Operational Areas (UNOA), Potential Release Location (PRL) 229 located at KSC. HydroGeoLogic, Inc. (HGL) prepared this report under Contract Number 80KSC019D0012. The purpose of the CSR is to provide information to evaluate the level of potential contamination in surface water and sediment samples collected from the RTDA PRL 229 Pond and determine if contaminants pose unacceptable risks to ecological receptors. The CSR provides analytical data of 10 sets of surface water and sediment samples collected in 2021. Surface water samples were analyzed for volatile organic compounds (VOCs), semi-volatile organic compounds (SVOCs), polynuclear aromatic hydrocarbon (PAHs), metals, hardness, and salinity, while sediment samples were analyzed for metals, total organic carbon (TOC), SVOCs, PAHs, and total petroleum hydrocarbons (TPH). The CSR includes a Screening Level Ecological Risk Assessment (SLERA) conducted under KSC’s Resource Conservation and Recovery Act (RCRA) Corrective Action Program to determine if unacceptable risks to ecological receptors exist at PRL 229 Pond. Metals and PAHs were detected in surface water samples, including detections of antimony, arsenic, barium, calcium, copper, lead, magnesium, thallium, zinc, anthracene, benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(g,h,i)perylene, benzo(k)fluoranthene, chrysene, dibenzo(a,h)anthracene, fluoranthene, indeno(1,2,3-c,d)pyrene and pyrene. Based on measured salinity (1.03 to 1.21 parts per thousand), the pond was identified as freshwater. Sediment analytical results also contained detections of metals and PAHs, including antimony, arsenic, barium, beryllium, cadmium, chromium, copper, lead, mercury, nickel, selenium, thallium, zinc, anthracene benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(g,h,i)perylene, benzo(k)fluoranthene, chrysene, dibenzo(a,h)anthracene, fluoranthene, indeno(1,2,3-c,d)pyrene and pyrene. Potential risks to ecological receptors were evaluated in accordance with the SLERA Work Plan and the Decision Process Document for the Resource Conservation and Recovery Act (RCRA) Corrective Action Program at KSC (DPD) (Geosyntec, 2019), and using the 2021 sediment and surface water analytical results. Potential ecological receptors evaluated in the SLERA include the aquatic community, benthic invertebrates, aquatic birds, and aquatic mammals. The SLERA included Steps 2a through 2c of the Ecological Risk Assessment (ERA) process in accordance with the DPD. Using multiple lines of evidence, the SLERA concluded that many of the detected analytes are present at concentrations similar to those in background or reference locations at KSC, and/or at concentrations that would not pose a significant risk to ecological communities. There are no screening values available for the avian community, and PAHs are bioaccumulative compounds. For this reason, food web modeling was completed as a supplement to Step 2c to provide a quantitative evaluation of this exposure pathway. Food web modeling indicates that PAHs are unlikely to pose a risk to birds exposed to site sediment and surface water. Based on the results of the SLERA, the contaminants in sediment and surface water pose no to minimal risk to the ecological communities that could live or forage at the site. Based on the results of the SLERA, no further study is recommended for the RTDA Pond at PRL 229.

Confirmation Sampling↗

Generating Cryogenic Lunar Simulants Within the Planetary Exploration & Astromaterials Research Laboratory

The Planetary Exploration & Astromaterials Research Laboratory (PEARL) aims to provides capabilities for the creation of—and research on—cryogenic lunar regolith simulants (CRS) containing surface volatile analytes. CRS represent regolith samples that might be collected from lunar Permanently Shadowed Regions (PSRs) during future missions. Handling CRS requires procedural and engineering development due to extremely cold (i.e. ≤ - 196°C) working temperatures. However, there is an imperative to understand the physical and chemical alteration of samples during collection, transport, and curation processes throughout the Artemis missions. The chemistries that will be encountered within the PSRs need to be understood based upon prior mission data analysis. The ability to utilize these techniques provides future tests that could be relevant to planetary protection applications regarding future robotic sample return.

Lunar↗

Volatiles in interplanetary dust particles and aerogels

Volatiles measured in 25 interplanetary dust particles (IDPs) are a mixture of both indigenous materials and contaminants associated with the collection and processing of the ODPs prior to analysis. Most IDPs have been collected in the stratosphere using a silicone oil/freon mixture (20:1 ratio) coated on collector plates. Studies have shown that silicone oil, freon and hexane residues remain with the ODPs, despite attempts to clean the IDPs. Analysis of the IDPs with the LMMS-technique produces spectra with a mixture of indigeneous and contaminants components. The contamination signal can be identified and removed; however, the contamination signal may obscure some of the indigeneous component's signal. Employing spectra stripping techniques, the indigenous volatile constituents associated with the IDPs can be identified. Volatiles are similar to those measured in CI or CM carbonaceous chondrites. Collection of IDPs in low-Earth orbit utilizing a Cosmic Dust Collection Facility attached to Space Station Freedom has been proposed. The low-density material aerogel has been proposed as a collection substrate for IDPs. Our studies have concentrated on identifying volatile contaminants that are associated with aerogel. We have found that solvents used for the preparation of aerogel remain in aerogel and methods must be developed for removing the entrapped solvents before aerogels can be used for an IDP collection substrate.

Gibson, E. K., Jr.↗

Autonomous Science: Simulated Solar System Mission to Enceladus, Icy Ocean Moon of Saturn

Future NASA missions to icy ocean worlds such as Europa, Titan, or Enceladus will collect mass spectrometry (MS) data from exospheres, atmospheres, and plume volatiles to assess their geochemistry and potential for microbial life1. These remote missions face challenges related to limited bandwidth, communication, and power, highlighting the need for science autonomy2 to prioritize data for timely downlink. We extend our previous work on machine learning (ML) biosignature detection from isotope ratio mass spectrometry (IRMS) data to distributed systems missions (DSM) by incorporating the ML and autonomous data quality control and prioritization code into an onboard decision-making platform. We use simulated orbital telemetry for eight orbiters around Enceladus with a mothership to illustrate an automated biosignature and novel seawater chemistry detection with data prioritization from MS analyses of volatile CO2.

Conor Williams↗

Trace elements in Apollo 15 samples - Implications for meteorite influx and volatile depletion on the moon

Five Apollo 15 soils and four rocks were examined by neutron activation analysis for 18 volatile and siderophile elements. The results obtained are initially interpreted in terms of local geologic problems at the Apollo 15 site. Implications bearing on the meteorite influx and volatile element depletion on the moon are then examined. Elbow Crater soil 15081, collected 65 m from the rim, contains a meteoritic component equivalent to 1.72% Cl material, similar to that at other lunar sites. Other soils are lower owing to dilution by fresh bedrock or talus from the Apennine Front. The moon-earth difference in volatile elements is discussed from the viewpoint of a difference in the efficiency of accretion from the solar nebula.

Morgan, J. W.↗

False Cape Data Collection Annex, Solid Waste Management Unit 113, Limited Resource Conservation and Recovery Act Facility Investigation Report, Kennedy Space Center, Florida

This Resource Conservation and Recovery Act (RCRA) Facility Investigation (RFI) Report summarizes groundwater investigation activities performed between July 2020 and October 2023 at the False Cape Data Collection Annex (FCDC) (Solid Waste Management Unit [SWMU] 113) located at Kennedy Space Center, Florida. The purpose of the RFI is to characterize the nature and extent of volatile organic compound (VOC)-contaminated groundwater at FCDC; evaluate the fate and transport of VOC contamination; collect sufficient data to evaluate potential future requirements for the site, such as corrective measures, long term monitoring, or No Further Action; and conduct a human health preliminary risk evaluation (PRE) based on the groundwater data.

False Cape Data Collection Annex↗

Chlorine Isotopic Compositions of Apatite in Apollo 14 Rocks: Evidence for Widespread Vapor-Phase Metasomatism on the Lunar Nearside ~4 Billion Years Ago

Compared to most other planetary materials in the Solar System, some lunar rocks display high delta (sup 37) Cl signatures. Loss of Cl in a H<<Cl environment has been invoked to explain the heavy signatures observed in lunar samples, either during volcanic eruptions onto the lunar surface or during large scale degassing of the lunar magma ocean. To explore the conditions under which Cl isotope fractionation occurred in lunar basaltic melts, five Apollo 14 crystalline samples were selected (14053,19, 14072,13, 14073,9, 14310,171 along with basaltic clast 14321,1482) for in situ analysis of Cl isotopes using secondary ion mass spectrometry. Cl isotopes were measured within the mineral apatite, with delta (sup 37) Cl values ranging from +14.6 ± 1.6 per mille to +40.0 ± 2.9 per mille. These values expand the range previously reported for apatite in lunar rocks, and include some of the heaviest Cl isotope compositions measured in lunar samples to date. The data here do not display a trend between increasing rare earth elements contents and delta (sup 37) Cl values, reported in previous studies. Other processes that can explain the wide inter- and intra-sample variability of delta (sup 37) Cl values are explored. Magmatic degassing is suggested to have potentially played a role in fractionating Cl isotope in these samples. Degassing alone, however, could not create the wide variability in isotopic signatures. Our favored hypothesis, to explain small scale heterogeneity, is late-stage interaction with a volatile-rich gas phase, originating from devolatilization of lunar surface regolith rocks ~4 billion years ago. This period coincides with vapor-induced metasomastism recorded in other lunar samples collected at the Apollo 16 and 17 landing sites, pointing to the possibility of widespread volatile-induced metasomatism on the lunar nearside at that time, potentially attributed to the Imbrium formation event.

apatit↗

Leonid's Particle Analyses from Stratospheric Balloon Collection on Xerogel Surfaces

Recovered from a stratospheric balloon above 20 km on 17-18 November 1998, at least eight candidate microparticles were collected and analyzed from low-density silica xerogel collection plates. Capture time at Leonids' storm peak was validated locally along the balloon trajectory by direct video imaging of meteor fluence up to 24/hr above 98% of the Earth's atmosphere. At least one 30 micron particle agrees morphologically to a smooth, unmelted spherule and compares most closely in non-volatile elemental ratios (Mg/Si, Al/Si, and Fe/Si) to compositional data in surface/ocean meteorite collections. A Euclidean tree diagram based on composition makes a most probable identification as a non-porous stratospherically collected particle and a least probable identification as terrestrial matter or an ordinary chondrite. If of extraterrestrial origin, the mineralogical class would be consistent with a stony (S) type of silicate, olivine [(Mg,Fe)2SiO4] and pyroxene [(Mg, Fe)Si!O3)--or oxides, herecynite [(Fe,Mg) Al2O4].

Noever, David↗