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At least 433 records · Page 24

Measurements of NO(x) and NO(y) concentrations and fluxes over Arctic tundra

Measurements of the atmospheric concentrations of NO, NO2, total NO(y), and O3 were made during the NASA Arctic Boundary Layer Expedition (ABLE 3A) at a remote location in a tundra bog ecosystem in southeastern Alaska during the growing season (July-August 1988). Concentrations of NO(x) and NO(y) were found to be very low compared to other remote continental sites, indicating that anthropogenic influences were small at this site during this time of year. The NO(y) emission rate from the soil were 0.13 +/- 0.05 x 10 exp 9 molecules/sq cm/s. Direct measurements of the flux of total NO(y) were made for the first time, indicating downward flux of NO(y) at all times of day, with maximum deposition of 2.5 +/- 0.9 x 10 exp 9 molecules/sq cm/s in the afternoon. Deposition of HNO3 appears to dominate the atmosphere/surface exchange of NO(y). The mean dry deposition rate of NO(y) to the tundra was 1.8 +/- 1.0 x 10 exp 9 molecules/sq cm/s.

Bakwin, Peter S.↗

New class of Si-based superlattices - Alternating layers of crystalline Si and porous amorphous Si(1-x)Ge(x) alloys

Superlattices consisting of alternating layers of crystalline Si and porous amorphous Si(1-x)Ge(x) have been fabricated. This is accomplished by first growing a Si/Si(0.7)Ge(0.3) superlattice by molecular beam epitaxy, followed by Ar-ion milling to form mesa structures, and finally by immersion in HF:HNO3:H2O. This solution creates a porous structure similar to that created by anodic etching, and a high selectivity is observed for the conversion of the alloy layers relative to the Si layers. The degree of selectivity is found to depend on alloy-layer thickness and strain. Superlattices have been fabricated from 1-micron wide mesas with Si(0.7)Ge(0.3) layers fully converted to 5-nm thick porous amorphous material.

Fathauer, R. W.↗

Absorption parameters of very dense molecular spectra for the HITRAN compilation

Cross sections for the heavy molecules CFC-11, CFC-12, CFC-13, CFC-14, CFC-22, CFC-113, CFC-114, CFC-115, CCl4, ClONO2, N2O5, HNO4, and HNO3 are included on the HITRAN 91 database. For many of these species, the cross sections vary by a factor of two between room temperature and temperatures near 210 K. The chemical importance of the heavy molecules, the quantitative accuracy of the HITRAN 91 cross sections, and the need for additional spectroscopic quantification are discussed.

Massie, S. T.↗

Vapor pressures of solid hydrates of nitric acid - Implications for polar stratospheric clouds

Thermodynamic data are presented for hydrates of nitric acid: HNO3.H2O, HNO3.2H2O, HNO3.3H2O, and a higher hydrate. Laboratory data indicate that nucleation and persistence of metastable HNO3.2H2O may be favored in polar stratospheric clouds over the slightly more stable HNO3.3H2O. Atmospheric observations indicate that some polar stratospheric clouds may be composed of HNO3.2H2O and HNO3.3H2O. Vapor transfer from HNO3.2H2O to HNO3.3H2O could be a key step in the sedimentation of HNO3, which plays an important role in the depletion of polar ozone.

Worsnop, Douglas R.↗

Stratospheric spectroscopy with the far-infrared spectrometer (FIRS-2) - Overview and recent results

The Smithsonian Astrophysical Observatory's program of balloon-borne stratospheric spectroscopic measurements is described, including instrumentation, recent scientific results, and future plans. The design and operation of the FIRS-2 far-infrared spectrometer is discussed. The current status of our efforts to recover mixing-ratio profiles with about 1 percent precision is presented. Representative recent results are shown giving mixing-ratio profiles from 20 to 50 km, selected from the suite HOCl, HCl, HF, NO2, N2O, HNO3, OH, HO2, H2O2, H2O (and isotopes), O2 (and isotopes), O3 (and isotopes), and CO2 (and isotopes). The utility of O2 and CO2 spectral lines for information on view angle or temperature and pressure is discussed. Future plans are mentioned, including the use of FIRS-2 on a balloon platform for UARS correlative measurements, the use of FIRS-2 on the NASA DC-8 platform for polar measurements, and the potential benefits of a FIRS instrument on a Shuttle platform.

Traub, Wesley A.↗

Measurement of atmospheric composition by the ATMOS instrument from Table Mountain Observatory

Following its first flight on board the Space Shuttle 'Challenger' as part of the Spacelab 3 payload, the Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument has been operated at the Jet Propulsion Laboratory's Table Mountain Observatory (TMO; 34.4 deg N, 117.7 deg W, 2.23 km altitude) in the San Gabriel Mountains of Southern California. With the delay in the resumption of regular Shuttle flights, ATMOS has acquired a large number of high-quality, high-resolution infrared solar absorption spectra, spanning a period between late-1985 and mid-1990. These spectra are being analyzed to derive the column abundances of several atmospheric species including O3, HCl, HF, and HNO3. Although limited in temporal coverage, the preliminary results for these gases are discussed here in the context of the requirement and contribution to be made by similar instruments in detecting long term changes in stratospheric composition.

Gunson, Michael R.↗

Laboratory simulations of PSC particle formation

The growth of type I polar stratospheric cloud (PSC) particles was investigated. Mixtures of water and nitric acid vapor were condensed at temperatures and pressures approximating those of the polar stratosphere. Mono-, di-, and trihydrates of nitric acid were observed in condensed solids. Results indicate that precursor vapor composition determines solid composition. As solids grew and aged a slow increase in HNO3 was observed and composition appeared to change towards that of the more thermodynamically stable nitric acid trihydrate (NAT). Results suggest that over ten hours may be required for PSC particles to reach NAT composition and equilibrium NAT vapor pressure. Recent observations may have been from young clouds whose condensed materials have not yet reached equilibrium.

Marti, James↗

Fabrication of luminescent porous silicon with stain etches and evidence that luminescence originates in amorphous layers

Simple immersion of Si in stain etches of HF:HNO3:H2O or NaNO2 in aqueous HF was used to produce films exhibiting luminescence in the visible similar to that of anodically-etched porous Si. All of the luminescent samples consist of amorphous porous Si in at least the near surface region. No evidence was found for small crystalline regions within these amorphous layers.

Fathauer, R. W.↗

Aircraft laser infrared absorption spectrometer (ALIAS) for polar ozone studies

The ALIAS instrument is a very high resolution (0.0003/cm) scanning, tunable diode laser spectrometer designed to make direct, simultaneous measurements of NO2, HNO3, HCl, CH4, and either O3 or N2O (including vertical profiles of CH4 and N2O) in the polar stratosphere at sub-part-per-billion level sensitivities over integration times from 3 to 30 s. Unique features include a sample inlet/throttle system designed to achieve near-isokinetic sampling, in PSC events, an in-flight wavelength reference cell rack, mechanical fringe-spoilers, a four-laser/four-detector dewar with 24-hr hold-time operating at a fixed temperature without electrical regulation, and in-flight fast correlation routines for spectral drift compensation prior to spectral addition. Instrument design and test flight results are discussed in the light of ALIAS's role in the Winter 1991 Arctic aircraft stratospheric ozone campaigns out of Fairbanks, Alaska, and Bangor, Maine.

Webster, C. R.↗

Surface areas and porosities of ices used to simulate stratospheric clouds

Surface areas, bulk densities, and porosities of ices formed at 85 or 200 K are measured to study the morphology of the vapor-deposited ices that have been used to simulate ice clouds in the laboratory. Surface areas are measured from the Brunauer, Emmett, and Teller (BET) analysis of absorption isotherms obtained at 72.2 K. Bulk densities and porosities are determined photogrammetrically. Results show that water ice and HNO3-H2O ice films deposited from the vapor at temperatures below 200 K exhibit large BET surface areas and are highly porous. For the ices annealed at temperatures above 200 K, external surface areas calculated from the observed particle sizes agree reasonably well with the BET areas, which indicates that the annealed ices are composed of nonporous particles and that the porosity of these ices is due to interstices among the particles.

Keyser, Leon F.↗

Ab initio study of the molecular structure and vibrational spectrum of nitric acid and its protonated forms

The equilibrium structures, harmonic vibrational frequencies, IR intensities, and relative energetics of HNO3 and its protonated form H2NO3+ were investigated using double-zeta plus polarization and triple-zeta plus polarization basis sets in conjunction with high-level ab initio methods. The latter include second-order Moller-Plesset perturbation theory, the single and double excitation coupled cluster (CCSD) methods, a perturbational estimate of the effects of connected triple excitations (CCSD(T)), and the self-consistent field. To determine accurate energy differences CCSD(T) energies were computed using large atomic natural orbital basis sets. Four different isomers of H2NO3+ were considered. The lowest energy form of protonated nitric acid was found to correspond to a complex between H2O and NO2+, which is consistent with earlier theoretical and experimental studies.

Lee, Timothy J.↗

The cryogenic limb array etalon spectrometer (CLAES) on UARS - Experiment description and performance

The design and the performance of the cryogenic limb array spectrometer (CLAES) aboard the NASA Upper Atmosphere Research Satellite are discussed. CLAES measures altitude profiles of temperature, pressure, O3, H2O, CH4, N2O, NO, NO2, N2O5, HNO3, ClONO2, HCl, CFC 11, CFC 12, and aerosol absorption coefficients for atmospheric layer between 10 and 60 km. Examples of atmospheric spectral emission profiles for a number of constituents are presented as well as responsivity and noise parameters.

Roche, A. E.↗

Microwave digestion preparation and ICP determination of boron in human plasma

A microwave digestion procedure, followed by Inductively Coupled Argon Plasma Spectroscopy, is described for the determination of boron (B) in human plasma. The National Institute of Standards and Technology (NIST) currently does not certify the concentration of B in any substance. The NIST citrus leaves 1572 (CL) Standard Reference Material (SRM) and wheat flour 1567a (WF) were chosen to determine the efficacy of digestion. CL and WF values compare favorably to those obtained from an open-vessel, wet digestion followed by ICP, and by neutron activation and mass spectrometric measurements. Plasma samples were oxidized by doubled-distilled ultrapure HNO3 in 120 mL PFA Teflon vessels. An MDS-81D microwave digestion procedure allows for rapid and relatively precise determination of B in human plasma, while limiting handling hazards and sources of contamination.

Ferrando, A. A.↗

Pourous Si(x)Ge(1-x) Layers Within Single Crystals Of Si

Layers of porous Si(x)Ge(1-x) buried within single crystals of Si formed by epitaxial growth of Si/Si(x)Ge(1-x)/Si structures followed by etching in solutions of HF:HNO3:H2O. Electroluminescence from these layers utilized in novel optoelectronic devices.

Fathauer, Robert W.↗

Modeling of the partitioning of reactive odd nitrogen in the lower stratosphere using aircraft measurements of NOy, NO, and other trace species

The objective of this research was to gain a more thorough understanding of the atmospheric processes which control the partitioning of species within the reactive nitrogen (NO(y)) reservoir in the lower stratosphere. This understanding is crucial to predicting ozone loss in the stratosphere. NO(y) is defined as NO + NO2 + HNO3 + N2O5 + ClONO2 + HO2NO2 + NO3 + particulate nitrate. The research focuses on deriving the partitioning among these species using the combined set of measurements from the NASA ER-2 aircraft during recent missions designed to study stratospheric ozone depletion.

Kawa, Stephan Randolph↗

Selective formation of porous silicon

A pattern of porous silicon is produced in the surface of a silicon substrate by forming a pattern of crystal defects in said surface, preferably by applying an ion milling beam through openings in a photoresist layer to the surface, and then exposing said surface to a stain etchant, such as HF:HNO3:H20. The defected crystal will preferentially etch to form a pattern of porous silicon. When the amorphous content of the porous silicon exceeds 70 percent, the porous silicon pattern emits visible light at room temperature.

Fathauer, Jones↗

Stalking the LREE-enriched component in ureilites

Ureilites contain a LREE-enriched component whose origin and identity are unknown, but which may have been introduced into 4.55 Ga olivine + pyroxene assemblages at various times in the period 4.55 - 3.74 Ga. This component is volumetrically minor, inhomogeneously distributed, and can be removed with concentrated HNO3, which suggests that it may be contained in minor, interstitial phases not previously recognized in ureilites. There is evidence, however, that not all of this component is leachable. Whole rock samples of Kenna, Novo Urei, and ALHA77257 form a Nd-143/Nd-144-Sm-147/Nd-144 line with a slope corresponding to an age of 3.74 Ga. Although this line could be a mixing line, with one end-member being the LREE-enriched component and the other being a 4.55 Ga olivine + pyroxene assemblage, the observation that a pyroxene separate from Kenna plots on the line suggests that the LREE-enriched component at least partially equilibrated with the olivine and pyroxene and that the line is an isochron. We performed a leaching experiment on Kenna, using various acids and concentrations, in an attempt to isolate the LREE-enriched component and differentiate between possible hosts for it, and to determine whether all of it is leachable. Our results suggest that most of the LREE-enriched component is surface-sited, rather than contained in a discrete mineral. However, some of it is not readily leachable because it equilibrated with Kenna olivine + pyroxene at 3.79 plus or minus 0.05 Ga.

Goodrich, Cyrena Anne↗

Nitrates in SNCs: Implications for the nitrogen cycle on Mars

Nitrogen is the second most abundant constituent of the Martian atmosphere, after CO2, present at a level of ca. 2.7 percent. Several authors have hypothesized that earlier in the planet's history, nitrogen was more abundant, but has been removed by processes such as exospheric loss from the atmosphere. However, an alternative sink for atmospheric nitrogen is the regolith; model calculations have predicted that, via the formation of NOx, HNO2 and HNO3 in the lower layers of the Martian atmosphere, the regolith might trap nitrite and nitrate anions, leading to the build-up of involatile nitrates. Integrated over 4.5 x 10(exp 9) yr, such a mechanism would contribute the equivalent of a layer of nitrates up to 0.3 cm thick distributed across the Martian surface. Features in thermal emission spectra of the surface of Mars have been interpreted tentatively as emanating from various anions (carbonates, bicarbonates, sulphates, etc.), and the presence of nitrates has also been addressed as a possibility. The identification of carbonates in SCN meteorites has allowed inferences to be drawn concerning the composition and evolution of the Martian atmosphere in terms of its carbon isotope systematics; if nitrites, nitrates, or other nitrogen-bearing salts could be isolated from SNC's, similar conclusions might be possible for an analogous nitrogen cycle. Nitrates are unstable, being readily soluble in water, and decomposed at temperatures between 50 C and 600 C, depending on composition. Any nitrates present in SNC's might be removed during ejection from the planet's surface, passage to Earth, or during the sample's terrestrial history, by weathering etc. The same might have been said for carbonates, but pockets of shock-produced glass (lithology C) from within the EET A79001 shergottite and bulk samples of other SNC contain this mineral, which did apparently survive. Nitrates occurring within the glassy melt pockets of lithology C in EET A79001 might likewise be protected. Lithology C glass was therefore selected for nitrate analysis, first by non-destructive infra red spectroscopy, and then by stepped combustion.

Grady, Monica M.↗