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At least 325 records · Page 18

Automated Desalting Apparatus

Because salt and metals can mask the signature of a variety of organic molecules (like amino acids) in any given sample, an automated system to purify complex field samples has been created for the analytical techniques of electrospray ionization/ mass spectroscopy (ESI/MS), capillary electrophoresis (CE), and biological assays where unique identification requires at least some processing of complex samples. This development allows for automated sample preparation in the laboratory and analysis of complex samples in the field with multiple types of analytical instruments. Rather than using tedious, exacting protocols for desalting samples by hand, this innovation, called the Automated Sample Processing System (ASPS), takes analytes that have been extracted through high-temperature solvent extraction and introduces them into the desalting column. After 20 minutes, the eluent is produced. This clear liquid can then be directly analyzed by the techniques listed above. The current apparatus including the computer and power supplies is sturdy, has an approximate mass of 10 kg, and a volume of about 20 20 20 cm, and is undergoing further miniaturization. This system currently targets amino acids. For these molecules, a slurry of 1 g cation exchange resin in deionized water is packed into a column of the apparatus. Initial generation of the resin is done by flowing sequentially 2.3 bed volumes of 2N NaOH and 2N HCl (1 mL each) to rinse the resin, followed by .5 mL of deionized water. This makes the pH of the resin near neutral, and eliminates cross sample contamination. Afterward, 2.3 mL of extracted sample is then loaded into the column onto the top of the resin bed. Because the column is packed tightly, the sample can be applied without disturbing the resin bed. This is a vital step needed to ensure that the analytes adhere to the resin. After the sample is drained, oxalic acid (1 mL, pH 1.6-1.8, adjusted with NH4OH) is pumped into the column. Oxalic acid works as a chelating reagent to bring out metal ions, such as calcium and iron, which would otherwise interfere with amino acid analysis. After oxalic acid, 1 mL 0.01 N HCl and 1 mL deionized water is used to sequentially rinse the resin. Finally, the amino acids attached to the resin, and the analytes are eluted using 2.5 M NH4OH (1 mL), and the NH4OH eluent is collected in a vial for analysis.

Spencer, Maegan K.↗

Understanding Differences in the Response to Composition Change as Simulated by CCMVal Models

Chemistry climate models (CCMs) have a common conceptual basis. Differences in implementation lead to differences in the stratospheric ozone response to changes in composition and climate. Although evaluation by CCMVal-2 identified strengths and weaknesses of participant models, the evaluation results were not used to discriminate among projections for future ozone evolution, at least in part because the overall diagnostic evaluation did not cleanly relate to the differences in CCM response. Here we use a subset of CCMVal diagnostics and additional analysis to understand the differences in response. In the upper stratosphere, differences in simulated temperature and total odd nitrogen prior to increases in chlorine loading explain the large differences in CCM sensitivity. In the lower atmosphere, there are two principle contributions to differences in CCM sensitivity to chlorine and climate change. First, differences in the lower stratospheric ClO affect simulated sensitivity to chlorine. CCMs with best transport performance match NDACC column HCl measurements at a broad range of latitudes. Other CCMs disagree with observations due to differences in total inorganic chlorine, partitioning between HCl and ClONO2, or both. Differences in ClONO2 are directly related to differences in simulated ClO. Second, although all CCMs predict increased tropical upwelling, the rate of increase varies and contributes to differences in tropical ozone and the 60N-60S column average.

Douglass, Anne R.↗

Electrochemical Evaluation of Stainless Steels in Acidified Sodium Chloride Solutions

This paper presents the results of an investigation in which several 300-series stainless steels (SS): AISI S30403 SS (UNS S30403), AISI 316L SS (UNS S31603), and AISI 317L SS (LINS S31703), as well as highly-alloyed: SS 254-SMO (UNS S32154), AL-6XN (N08367) and AL29-4C (UNS S44735), were evaluated using DC electrochemical techniques in three different electrolyte solutions. The solutions consisted of neutral 3.55% NaCl, 3.55% NaCl in 0.1N HCl, and 3.55% NaCl in 1.0N HCl. These solutions were chosen to simulate environments that are less, similar, and more aggressive, respectively, than the conditions at the Space Shuttle launch pads. The electrochemical test results were compared to atmospheric exposure data and evaluated for their ability to predict the long-term corrosion performance of the subject alloys. The electrochemical measurements for the six alloys indicated that the higher-alloyed SS 254-SMO, AL29-4C, and AL-6XN exhibited significantly higher resistance to localized corrosion than the 300-series SS. There was a correlation between the corrosion performance of the alloys during a two-year atmospheric exposure and the corrosion rates calculated from electrochemical (polarization resistance) measurements.

Calle, L. M.↗

Energy Distribution among Reaction Products. III: The Method of Measured Relaxation Applied to H + Cl2

The method of measured relaxation is described for the determination of initial vibrational energy distribution in the products of exothermic reaction. Hydrogen atoms coming from an orifice were diffused into flowing chlorine gas. Measurements were made of the resultant ir chemiluminescence at successive points along the line of flow. The concurrent processes of reaction, diffusion, flow, radiation, and deactivation were analyzed in some detail on a computer. A variety of relaxation models were used in an attempt to place limits on k(nu prime), the rate constant for reaction to form HCl in specified vibrational energy levels: H+Cl2 yields (sup K(nu prime) HCl(sub nu prime) + Cl. The set of k(?) obtained from this work is in satisfactory agreement with those obtained by another experimental method (the method of arrested relaxation described in Parts IV and V of the present series.

Pacey, P. D.↗

Multi-Decadal Records of Stratospheric Composition and Their Relationship to Stratospheric Circulation Change

Constituent evolution for 1990-2015 simulated using the Global Modeling Initiative chemistry and transport model driven by meteorological fields from the Modern-Era Retrospective analysis for Research and Applications version 2 (MERRA-2) is compared with three sources of observations: ground-based column measurements of HNO3 and HCl from two stations in the Network for the Detection of Atmospheric Composition Change (NDACC, 1990- ongoing), profiles of CH4 from the Halogen Occultation Experiment (HALOE) on the Upper Atmosphere Research Satellite (UARS, 1992-2005), and profiles of N2O from the Microwave Limb Sounder on the Earth Observing System satellite Aura (2005- ongoing). The differences between observed and simulated values are shown to be time dependent, with better agreement after 2000 compared with the prior decade. Furthermore, the differences between observed and simulated HNO3 and HCl columns are shown to be correlated with each other, suggesting that issues with the simulated transport and mixing cause the differences during the 1990s and that these issues are less important during the later years. Because the simulated fields are related to mean age in the lower stratosphere, we use these comparisons to evaluate the time dependence of mean age. The ongoing NDACC column observations provide critical information necessary to substantiate trends in mean age obtained using fields from MERRA-2 or any other reanalysis products.

Profiles of N2O from the Microwave Limb Sounde↗

Analysis of Seed Sanitization, Rapid Freezer Proficiency, and Veg-03 Water Verification

In order to ensure the well-being of astronauts and experiments on the ISS (International Space Station), seeds need to be free of microbes, the rapid freezer needs to be freezing biological samples evenly and proficiently, and the astronauts need to have accurate watering procedures for Veg-03 (the latest Phytotron for the Veggie (Vegetable Production System) project). Seed flight candidates were sanitized with varying levels of HCL in order to determine the right amount to use for future flight experiments, too much HCL and the seeds will not germinate and too little and they will be contaminated with microorganisms. The rapid freezer was assessed using temperature probes to determine if there is a homogeneous change in temperature in order to ensure the safe freezing of biological organisms. The plant watering procedures given to the astronauts were assessed in order to make sure that Veg-03 experiments are receiving the correct amount of water.

Hollingsworth, Savannah↗

EOS Microwave Limb Sounder observations of the Antarctic polar vortex breakup in 2004

New observations from the Microwave Limb Sounder (MLS) on NASA’s Aura satellite give a detailed picture of the spring Antarctic polar vortex breakup throughout the stratosphere, with the first daily global HCl profiles providing an unprecedentedly clear view of transport in the lower stratosphere. Poleward transport at progressively lower levels, filamentation, and mixing are detailed in MLS HCl, N2O, H2O, and O3 as the 2004 Antarctic vortex broke up from the top down in early October through late December. Improved MLS H2O data show the subvortex, below the tropical tropopause, breaking up almost simultaneously with the lower stratospheric vortex in December. Vortex remnants persisted in MLS tracers for over a month after the breakup in the midstratosphere, but no more than a week in the lower stratosphere. MLS observations show diabatic descent continuing throughout November, but weak ascent after late October in the lower stratospheric vortex core. Our results extend previous observational transport studies and show consistency with mixing and vortex evolution in meteorological analyses, and with model studies

Pawson, S.↗

Fire Safety Implications of Preliminary Results from Saffire IV and V Experiments on Large Scale Spacecraft Fires

The spread and growth of flames over large solid fuel samples and their effect on the pressurized spacecraft were studied inside the Cygnus spacecraft while in orbit after departing the International Space Station. These experiments were developed by NASA’s Advanced Exploration Systems Division in the Human Exploration and Operations Mission Directorate. The ignited materials consisted of poly-methyl methacrylate (PMMA), cotton fabric and a cotton/fiberglass fabric blend. The samples were all 40 cm wide and with various lengths ranging from 18 cm for the PMMA samples to 50 cm for the fabrics. The overall results from these tests and their impact on the spacecraft are presented with emphasis on the fire safety implications of the results. The experiments included, a post-fire cleanup system, vehicle internal volume measurements, and transport of acid gases (HCl and HF). Measurements included video images, flame spread rate, flame temperatures and radiant heat output; energy release through oxygen calorimetry; distributed measurements of CO2 concentration and temperature at six locations in the spacecraft; CO2, CO, O2, HF and HCl concentrations; vehicle pressurized volume; and aerosol concentrations. Details of the flame growth and spread are discussed in other papers as are details of the post-fire cleanup system performance. The fire events had a measurable impact on the vehicle pressure, temperature, and carbon dioxide concentration. However, despite having heat release rates up to 10 kW, the average vehicle conditions did not rise to unacceptable levels. The combined results of the experiments provide significant new understanding of the impact of sample and flow duct height on flame spread and growth in addition to an improved perspective of the impact of a fire event on a spacecraft.

micorgravity↗

Probing the Atmospheric Cl Isotopic Ratio on Mars: Implications for Planetary Evolution and Atmospheric Chemistry

Following the recent detection of HCl in the atmosphere of Mars by ExoMars/Trace Gas Orbiter, we present here the first measurement of the 37Cl/35Cl isotopic ratio in the Martian atmosphere using a set of NOMAD observations. We determine an isotopic anomaly of -6 ±78‰ compared to Earth standard, consistent with the -51‰ to -1‰ measured on Mars’ surface by Curiosity. The measured isotopic ratio is also consistent with surface measurements, and suggests that Cl reservoirs may have undergone limited processing since formation in the Solar Nebula. The examination of possible sources and sinks of HCl shows only limited pathways to short-term efficient Cl fractionation and many plausible reservoirs of “light” Cl.

Exomars NOMAD↗

Fire Safety Implications of Preliminary Results from Saffire IV and V Experiments on Large Scale Spacecraft Fires

The spread and growth of flames over large solid fuel samples and their effect on the pressurized spacecraft were studied inside the Cygnus spacecraft while in orbit after departing the International Space Station. These experiments were developed by NASA’s Advanced Exploration Systems Division in the Human Exploration and Operations Mission Directorate. The ignited materials consisted of poly-methyl methacrylate (PMMA), cotton fabric and a cotton/fiberglass fabric blend. The samples were all 40 cm wide and with various lengths ranging from 18 cm for the PMMA samples to 50 cm for the fabrics. The overall results from these tests and their impact on the spacecraft are presented with emphasis on the fire safety implications of the results. The experiments included, a post-fire cleanup system, vehicle internal volume measurements, and transport of acid gases (HCl and HF). Measurements included video images, flame spread rate, flame temperatures and radiant heat output; energy release through oxygen calorimetry; distributed measurements of CO2 concentration and temperature at six locations in the spacecraft; CO2, CO, O2, HF and HCl concentrations; vehicle pressurized volume; and aerosol concentrations. Details of the flame growth and spread are discussed in other papers as are details of the post-fire cleanup system performance. The fire events had a measurable impact on the vehicle pressure, temperature, and carbon dioxide concentration. However, despite having heat release rates up to 10 kW, the average vehicle conditions did not rise to unacceptable levels. The combined results of the experiments provide significant new understanding of the impact of sample and flow duct height on flame spread and growth in addition to an improved perspective of the impact of a fire event on a spacecraft.

microgravity fire safety↗

Soluble Organic Matter (SOM) analysis of the Hayabusa2 samples: The first results

The Hayabusa2 spacecraft successfully collected the surface and possible sub-surface materials of the asteroid 162173 Ryugu. Ryugu is a C-type asteroid characterized by a low-albedo surface probably consisting of hydrous minerals and carbonaceous materials. [1] The direct optical and spectral analysis of the returned samples indicates that Ryugu material is dominated by hydrous carbonaceous chondrite-like matter (similar to CI chondrites) [2]. Since carbonaceous chondrites have generally yielded various types of organic matter, the collected Ryugu grains are expected to contain diverse types of organic compounds including bio-related molecules. The occurrence of organic compounds in the Ryugu surface will provide clues to the evolution of prebiotic molecules and their preservations associated with aqueous alteration of the primitive asteroid. The initial analysis of soluble organic matter (SOM) of the Hayabusa2-returned samples has been performed by an international team consisting of 32 members. Because the sample amount available for comprehensive SOM analyses is limited, and because the SOM is expected to be present as a complex mixture of various types of organic compounds with very small concentrations of each compound, high-sensitivity and high-resolution analytical techniques have been developed using carbonaceous meteorites [e.g. 3]. Two aggregate samples of the Ryugu grains (A106 and C107) were allocated for the solvent extractions and bulk carbon (C), hydrogen (H), nitrogen (N), sulfur (S) and oxygen (O) measurements. The A106 sample was collected during the 1st sampling in February 2019 and the C107 sample was collected during the 2nd sampling in July 2019 after the Small Carry Impactor (SCI) operation. They consist mainly of particles smaller than 1 mm in diameter, and each sample mass was 38-39 mg. They were firstly investigated spectroscopically in the near infrared wavelength range by the Stone Team prior to the solvent extractions. Other small grains (A0080 and C0057) were also allocated for this study to investigate the spatial distribution of organic compounds on the sample surface. The extraction and analytical measurements implemented by the SOM Team are summarized in Figure 1. Each powder sample was extracted sequentially with non-polar to polar solvents, i.e., hexane, dichloromethane (DCM), methanol (MeOH) and H2O, for non-targeted analysis to reveal the compound composition. Each solvent extract was analyzed by solution state nuclear magnetic resonance (NMR) spectroscopy [4], Fourier transform- ion cyclotron resonance/mass spectrometry (FT-ICR/MS) with ESI and APPI ionization [5] and by high-resolution mass spectroscopy using Orbitrap MS coupled with nano-liquid chromatography (nanoLC/Orbitrap MS) [6], and using two dimensional gas chromatography/mass spectrometry (GC×GC/MS). The extracted residues were passed to the Chemistry Team for further inorganic element analysis. The other powder sample was subjected to the hot water extraction for amino acid analyses including chiral isomer separation, which was performed by three-dimensional (3D) high-performance liquid chromatography (HPLC) with high-sensitivity fluorescence detection (FD) [7] and by HPLC/FD coupled with quadrupole-time of flight/mass spectrometry (QToF/MS) [8]. After the hot water extraction, the residue was split into two halves. One half was further extracted with hydrochloric acid (HCl) to analyze for amino acids in bound-form. The other half was sequentially extracted with DCM/MeOH (1/1) to analyze semi-polar compounds such as polycyclic aromatic hydrocarbons (PAHs) by GC/MS, followed by further extraction with formic acid to analyze polar heterocyclic compounds, and subsequent extraction with HCl to detect bound-form polar compounds. The extracted residues were passed to the IOM Team for the analysis of insoluble organic matter (IOM). Compound-specific stable isotope analyses will be performed using GC/combustion/isotope ratio mass spectrometry (GC/C/IRMS) if the compound concentration is high enough to enable such an isotopic measurement. All extraction procedures were performed on an ISO 6 (Class 100) clean bench inside an ISO 5 (Class 1000) clean room. Baked serpentine powder was also analyzed as a procedural blank. In situ organic compound analysis with the molecular imaging was performed using desorption electrospray ionization (DESI) equipped with Orbitrap MS [9, 10], followed by spatial imaging of organic compounds using ToF/secondary ion mass spectrometry (ToF/SIMS) [11]. The bulk chemical and isotopic compositions of CNS and HO were determined using nano-elemental analysis/isotope ratio mass spectrometry (nanoEA/IRMS) [12] and EA/pyrolysis/IRMS, respectively. We have identified a variety of indigenous organic compounds in the extracts of both A106 and C107 samples. The Ryugu grains host organic molecules under the high-vacuum and cosmic-ray irradiation environment of the asteroid surface. The analysis of extracted molecules is in progress, and the first results will be presented at the symposium.

Hiroshi Naraoka↗

Growth of Lower Stratospheric HCl/Cly Since 1993: Observations from Aircraft (ALIAS), Balloon (MarkIV, FIRS-2), Space Shuttle (ATMOS), and Satellite (HALOE) Measurements

Measurements of HCl in the lower stratosphere (15-21 km) from aircraft, balloon, Space Shuttle, and satellite reveal a growth in its mean abundance relative to that of total inorganic chlorine (Cly) from HCl/Cly = 57(+/-5)% in early 1993 to 75(+/-7)% by the end of 1997.

HCl lower stratosphere inorganic chlorine ATMOS HA↗

Improved process for synthesizing anilinosilane compounds

New process gives good yields of anilinosilane compounds that can be readily isolated in a high state of purity. S-collidine is used as an HCl acceptor. Silane compounds can be melt-condensed with aromatic diols to provide high molecular weight polyaryloxysilane materials that are of importance in polymer technology.

Dunnavant, W. R.↗