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At least 433 records · Page 24

Simultaneous, in situ measurements of OH, HO2, O3, and H2O - A test of modeled stratospheric HO(x) chemistry

Simultaneous, in situ measurements of OH, HO2, H2O, and O3 from 37-23 km are reported. The partitioning between OH and HO2 and the total HO(x) concentration are compared with expected steady-state values. The ratio of HO2 to OH varies from less than 2 at 36 km to more than 3 at 25 km; in the lower stratosphere this ratio is nearly a factor of two less than predicted. The data are used to calculate HO(x) production and loss rates. The measured HO(x) mixing ratio is consistent with production dominated by the reaction of O(1D) with H2O, and loss controlled by NOy below 28 km and HO(x) above 30 km. The steady-state concentration of H2O2 is inferred from the measured HO2 concentration and calculated photolysis rate. The maximum H2O2 mixing ratio (at 33 km) is predicted to be less than 0.2 ppb.

Wennberg, P. O.↗

Dual-throat thruster thermal model

The dual-throat engine is one of the dual nozzle engine concepts studied for advanced space transportation applications. It provides a thrust change and an in-flight area ratio change through the use of two concentric combustors with their throats arranged in series. Test results are presented for a dual throat thruster burning gaseous oxygen and hydrogen at primary (inner) chamber pressures from 380 to 680 psia. Heat flux profiles were obtained from calorimetric cooling channels in the inner nozzle, outer or secondary chamber and the tip of the inner nozzle. Data were obtained for two nozzle spacings over a chamber pressure ratio (secondary/primary) range of 0.45 to 0.83 with both chambers firing (Mode I). Fluxes near the end of the inner nozzle were significantly higher than in Mode II when only the inner chamber was fired, due to the flow separation and recirculation caused by the back pressure imposed by the secondary chamber. As the pressure ratio increased, these heat fluxes increased and the region of high heat flux relative to Mode II extended farther upstream. The use of the gaseous hydrogen bleed flow in the secondary chamber to control heat fluxes in the primary plume attachment region was investigated in Mode II testing. A thermal model of a dual throat thruster was developed and upgraded using the experimental data.

Ewen, R. L.↗

New Reduced Two-Time Step Method for Calculating Combustion and Emission Rates of Jet-A and Methane Fuel With and Without Water Injection

A simplified kinetic scheme for Jet-A, and methane fuels with water injection was developed to be used in numerical combustion codes, such as the National Combustor Code (NCC) or even simple FORTRAN codes that are being developed at Glenn. The two time step method is either an initial time averaged value (step one) or an instantaneous value (step two). The switch is based on the water concentration in moles/cc of 1x10(exp -20). The results presented here results in a correlation that gives the chemical kinetic time as two separate functions. This two step method is used as opposed to a one step time averaged method previously developed to determine the chemical kinetic time with increased accuracy. The first time averaged step is used at the initial times for smaller water concentrations. This gives the average chemical kinetic time as a function of initial overall fuel air ratio, initial water to fuel mass ratio, temperature, and pressure. The second instantaneous step, to be used with higher water concentrations, gives the chemical kinetic time as a function of instantaneous fuel and water mole concentration, pressure and temperature (T4). The simple correlations would then be compared to the turbulent mixing times to determine the limiting properties of the reaction. The NASA Glenn GLSENS kinetics code calculates the reaction rates and rate constants for each species in a kinetic scheme for finite kinetic rates. These reaction rates were then used to calculate the necessary chemical kinetic times. Chemical kinetic time equations for fuel, carbon monoxide and NOx were obtained for Jet-A fuel and methane with and without water injection to water mass loadings of 2/1 water to fuel. A similar correlation was also developed using data from NASA's Chemical Equilibrium Applications (CEA) code to determine the equilibrium concentrations of carbon monoxide and nitrogen oxide as functions of overall equivalence ratio, water to fuel mass ratio, pressure and temperature (T3). The temperature of the gas entering the turbine (T4) was also correlated as a function of the initial combustor temperature (T3), equivalence ratio, water to fuel mass ratio, and pressure.

Molnar, Melissa↗

Simplified Two-Time Step Method for Calculating Combustion and Emission Rates of Jet-A and Methane Fuel With and Without Water Injection

A simplified kinetic scheme for Jet-A, and methane fuels with water injection was developed to be used in numerical combustion codes, such as the National Combustor Code (NCC) or even simple FORTRAN codes. The two time step method is either an initial time averaged value (step one) or an instantaneous value (step two). The switch is based on the water concentration in moles/cc of 1x10(exp -20). The results presented here results in a correlation that gives the chemical kinetic time as two separate functions. This two time step method is used as opposed to a one step time averaged method previously developed to determine the chemical kinetic time with increased accuracy. The first time averaged step is used at the initial times for smaller water concentrations. This gives the average chemical kinetic time as a function of initial overall fuel air ratio, initial water to fuel mass ratio, temperature, and pressure. The second instantaneous step, to be used with higher water concentrations, gives the chemical kinetic time as a function of instantaneous fuel and water mole concentration, pressure and temperature (T4). The simple correlations would then be compared to the turbulent mixing times to determine the limiting rates of the reaction. The NASA Glenn GLSENS kinetics code calculates the reaction rates and rate constants for each species in a kinetic scheme for finite kinetic rates. These reaction rates are used to calculate the necessary chemical kinetic times. Chemical kinetic time equations for fuel, carbon monoxide and NOx are obtained for Jet-A fuel and methane with and without water injection to water mass loadings of 2/1 water to fuel. A similar correlation was also developed using data from NASA's Chemical Equilibrium Applications (CEA) code to determine the equilibrium concentrations of carbon monoxide and nitrogen oxide as functions of overall equivalence ratio, water to fuel mass ratio, pressure and temperature (T3). The temperature of the gas entering the turbine (T4) was also correlated as a function of the initial combustor temperature (T3), equivalence ratio, water to fuel mass ratio, and pressure.

Molnar, Melissa↗

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.↗

Rb-Sr systematics for chemically defined Apollo 15 and 16 materials

Concentrations of Rb and Sr and the Sr87/86 ratios are determined in a large number of Apollo 15 samples, including KREEP basalts, mare basalts, anorthosite breccia clasts, lithic fragments, a spinel-bearing clast, green glass samples, breccia matrix, and soils. Relative concentrations of Sm, Eu, Rb, and Sr are also examined in the samples, with particular attention to Rb/Sr systematics vs other trace element abundances and total chemical compositions of rocks. Analysis of crystalline KREEP samples rich in trace elements indicates that the differentiation of these rocks has extended to -4.25 AE age, a significantly later time than the presumed time of accretion of the moon.

Nyquist, L. E.↗

Protein Crystallization Using Room Temperature Ionic Fluids

The ionic liquids (ILs) 1-butyl-3-methylimidizolium chloride (C4mim-C1), 1-butyl-3- methylimidizolium diethyleneglycol monomethylethersulfate ([C4mim]DEMGS), and 1-butyl-1 -methylpyrollidinium dihydrogenphosphate ([p1,4]dhp) were tested for their effects on the crystallization of the proteins canavalin, beta-lactoglobulin B, xylanase, and glucose isomerase, using a standard high throughput screen. The crystallization experiments were set up with the ILs added to the protein solutions at 0.2 and 0.4 M final concentrations. Crystallization droplets were set up at three proteixprecipitant ratios (1:1, 2:1, and 4:l), which served to progressively dilute the effects of the screen components while increasing the equilibrium protein and IL concentrations. Crystals were obtained for all four proteins at a number of conditions where they were not obtained from the IL-free control experiment. Over half of the protein-IL combinations tested had more successful outcomes than negative, where the IL-free crystallization was better than the corresponding IL-containing outcome, relative to the control. One of the most common causes of a negative outcome was solubilization of the protein by the IL, resulting in a clear drop. In one instance, we were able to use the IL-induced solubilizing to obtain beta-lactoglobulin B crystals from conditions that gave precipitated protein in the absence of IL. The results suggest that it may be feasible to develop ILs specifically for the task of macromolecule crystallization.

Pusey, Marc L.↗

Biooptical variability in the Greenland Sea observed with the Multispectral Airborne Radiometer System (MARS)

A site-specific ocean color remote sensing algorithm was developed and used to convert Multispectral Airborne Radiometer System (MARS) spectral radiance measurements to chlorophyll-a concentration profiles along aircraft tracklines in the Greenland Sea. The analysis is described and the results given in graphical or tabular form. Section 2 describes the salient characteristics and history of development of the MARS instrument. Section 3 describes the analyses of MARS flight segments over consolidated sea ice, resulting in a set of altitude dependent ratios used (over water) to estimate radiance reflected by the surface and atmosphere from total radiance measured. Section 4 presents optically weighted pigment concentrations calculated from profile data, and spectral reflectances measured in situ from the top meter of the water column; this data was analyzed to develop an algorithm relating chlorophyll-a concentrations to the ratio of radiance reflectances at 441 and 550 nm (with a selection of coefficients dependent upon whether significant gelvin presence is implied by a low ratio of reflectances at 410 and 550 nm). Section 5 describes the scaling adjustments which were derived to reconcile the MARS upwelled radiance ratios at 410:550 nm and 441:550 nm to in situ reflectance ratios measured simultaneously on the surface. Section 6 graphically presents the locations of MARS data tracklines and positions of the surface monitoring R/V. Section 7 presents stick-plots of MARS tracklines selected to illustrate two-dimensional spatial variability within the box covered by each day's flight. Section 8 presents curves of chlorophyll-a concentration profiles derived from MARS data along survey tracklines. Significant results are summarized in Section 1.

Mueller, James L.↗

Application of OMI Observations to a Space-Based Indicator of NOx and VOC Controls on Surface Ozone Formation

We investigated variations in the relative sensitivity of surface ozone formation in summer to precursor species concentrations of volatile organic compounds (VOCs) and nitrogen oxides (NOx) as inferred from the ratio of the tropospheric columns of formaldehyde to nitrogen dioxide (the "Ratio") from the Aura Ozone Monitoring Instrument (OMI). Our modeling study suggests that ozone formation decreases with reductions in VOCs at Ratios less than 1 and NOx at Ratios greater than 2; both NOx and VOC reductions may decrease ozone formation for Ratios between 1 and 2. Using this criteria. the OMI data indicate that ozone formation became: 1. more sensitive to NOx over most of the United States from 2005 to 2007 because of the substantial decrease in NOx emissions, primarily from stationary sources, and the concomitant decrease in the tropospheric column of NO2. and 2. more sensitive to NOx with increasing temperature, in part because emissions of highly reactive, biogenic isoprene increase with temperature, thus increasing the total VOC reactivity. In cities with relatively low isoprene emissions (e.g .. Chicago). the data clearly indicate that ozone formation became more sensitive to NOx from 2005 to 2007. In cities with relatively high isoprene emissions (e.g ., Atlanta), we found that the increase in the Ratio due to decreasing NOx emissions was not obvious as this signal was convolved with variations in the Ratio associated with the temperature dependence of isoprene emissions and, consequently, the formaldehyde concentration.

Duncan, Bryan N.↗

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↗

Photosynthetic Gas Exchange in the Closed Ecosystem for Space. Phase II, Part II. Studies on the Growth of Thermophilic Chlorella 71105

Bench-scale studies with Chlorella pyrenoidosa 71105 were conducted in four- and eight-liter culture vessels, with and without recycling. It was established that the algal strain could be maintained for periods up to 72 days with supplemented re-cycled medium. In a factorial series of experiments, the highest yields were obtained with a 2.0% concentration of carbon dioxide, a 0.07 dilution factor (nutrient dilution rate/culture volume), and an 8.5 ft(exp -1) ratio of light surface to liquid culture volume. Optimum pH and concentrations of the constituents of the growth medium were determined in corollary test-tube studies. Other test-tube studies showed that the nutrient medium used for mass culture could be stored up to five weeks at 25 C or at refrigerator temperature (4 C) with little change in nitrogen-urea level. Algal suspensions stored at 4 C remained viable for periods of at least 12 weeks; growth resumed after a lag period when stored suspensions were cultured at 39 C. Streptomycin was found suitable for controlling a blue-green containment.

ALGAE↗

Design of nonimaging concentrators as second stages in tandem with image-forming first-stage concentrators

The paper discusses the paraboloidal mirror as a tracking solar concentrator, fitting a nonimaging second stage to the paraboloidal mirror, other image-forming systems as first stages, and tracking systems in two-dimensional geometry. Because of inherent aberrations, the paraboloidal mirror cannot achieve the thermodynamic limit. It is shown how paraboloidal mirrors of short focal ratio and similar systems can have their flux concentration enhanced to near the thermodynamic limit by the addition of nonimaging compound elliptical concentrators.

Winston, R.↗

Analysis of high altitude remotely sensed data collected in the Nantucket Shoals experiment 4-15 May, 1981

High altitude ocean color scanner ratios of band 2 (456 to 476 nanometers) to band 4 (539 to 559 nanometers) and band 1 (418 to 438 nanometers) to band 3 (498 to 518 nanometers) had high correlation coefficient values (-0.928 and 0.891 respectively) with seven boat sampled chlorophyll a measurements. The range of chlorophyll a concentrations was small (1.7-2.58 mg/cu m.). Each ratio was used to calculate chlorophyll a values for the center pixel of each scan line on flight lines 5 and 6. The two ratios produced dissimilar chlorophyll a trends. Due to the high noise level in the scanner data, no reliable synoptic chlorophyll a map could be generated with either ratio algorithm.

Ohlhorst, C. W.↗

Deuterium Isotope Fractionation of Polycyclic Aromatic Hydrocarbons in Meteorites as an Indicator of Interstellar/Protosolar Processing History

The stable isotope composition of soluble and insoluble organic compounds in carbonaceous chondrites can be used to determine the provenance of organic molecules in space. Deuterium enrichment in meteoritic organics could be a residual signal of synthetic reactions occurring in the cold interstellar medium or an indicator of hydrothermal parent-body reactions. δD values have been measured in grains and bulk samples for a wide range of meteorites; however, these reservoirs are highly variable and may have experienced fractionation during thermal and/or aqueous alteration. Among the plethora of organic compounds in meteorites are polycyclic aromatic hydrocarbons (PAHs), which are stable and abundant in carbonaceous chondrites, and their δD ratio may preserve evidence about their formation environment as well as the influence of parent-body processes. This study tests hypotheses about the potential links between PAHs-deuteration concentrations and their formation conditions by examining the δD ratio of PAHs in three CM carbonaceous chondrites representing an aqueous alteration gradient. We use deuterium enrichments in soluble 2–5-ring PAHs as an indicator of either photon-driven deuteration due to unimolecular photodissociation in warm regions of space, gas-phase ion–molecule reactions in cold interstellar regions of space, or UV photolysis in ices. We also test hypothesized reaction pathways during parent-body processing that differ between partially and fully aromatized PAHs. New methodological approaches were developed to extract small, volatile PAHs without fractionation. Our results suggest that meteoritic PAHs could have formed through reactions in cold regions, with possible overprinting of deuterium enrichment during aqueous parent-body alteration, but the data could not rule out PAH alteration in icy mantles as well.

H V Graham↗

Fluid-Evaporation Records Preserved in Meridiani Rocks

We have shown earlier that the high SO3/Cl ratios found in secondary mineral assemblages in shergottite GRIM glasses (Gas-Rich Impact-Melt) likely resulted from interactions of regolith materials with sulfate-rich (and Cl-poor) solutions. The low SO3/Cl ratios determined in secondary salts in nakhalite fracture-fillings presumably formed by rock interactions with chloride-rich (and SO4-poor) solutions near Mars surface. The SO3 and Cl abundances determined by APXS in abraded rocks (RAT) from Endurance, Fram and Eagle craters indicate that these salt assemblages likely formed by evaporative concentration of brine fluids at Meridiani. The SO3/Cl ratios in the abraded rocks are examined here, instead of their absolute abundances, because the abundance ratios might provide better guide-lines for tracking the evolution of evaporating fluids at Meridiani. The SO3/Cl ratios in these samples, in turn, might provide clues for the mobile element ratios of the altering fluids that infiltrated into the Meridiani rocks.

Rao, M. N.↗

Venus cloud properties: Infrared opacity and mass mixing ratio

By using the Mariner 5 temperature profile and a homogeneous cloud model, and assuming that CO2 and cloud particles are the only opacity sources, the wavelength dependence of the Venus cloud opacity is inferred from the infrared spectrum of the planet between 450 and 1250/cm. Justification for applying the homogeneous cloud model is found in the fact that numerous polarization and infrared data are mutually consistent within the framework of such a model; on the other hand, dense cloud models are not satisfactory. Volume extinction coefficients varying from 0.000005 to 0.000015/cm depending on the wavelength, are determined at the tropopause level of 6110 km. By using all available data, a cloud mass mixing ratio of approximately 0.000005 and a particle concentration of about 900 particles per cu cm at this level are also inferred. The derived cloud opacity compares favorably with that expected for a haze of droplets of a 75% aqueous solution of sulfuric acid.

Samuelson, R. E.↗