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NASA NTRS1993

Al-26-Mg-26 ages of iron meteorites

An exposure age for an iron meteorite can be calculated from measurements of a radioactive nuclide and a stable nuclide that are produced by similar sets of nuclear reactions, provided that the stable nuclide is present with low initial abundance. The standard methods rely on either K-40 (t(sub 1/2) = 1.26 Gy), K-39, and K-41 or on a shorter-lived radionuclide and a stable, noble gas isotope. Widely used pairs of this type include Cl-36/Ar-36 and Al-26/Ne-21. Other pairs that may serve the purpose for iron meteorites contain many stable isotopes besides those of K and the noble gases that are produced partly by cosmic rays. We consider here the calculation of exposure ages, t(sub 26), from measurements of Al-26 (t(sub 1/2) = 0.7 My) and (stable) Mg-26. Ages based on Al-26/Mg-26 ratios, like those based on Cl-36/Ar-36 ratios, are 'buffered' against changes in relative production rates due to shielding because decay of the radioactive nuclide accounts for a good part of the inventory of the stable nuclide.

Herzog, G. F.↗
NASA NTRS1993

Al-26 production profile and model comparisons in Canyon Diablo

The large preatmospheric size of the Canyon Diablo meteorite, a radius of about 15 m, makes it especially suitable for systematic studies of cosmogenic nuclide production rates of iron objects in a 2 pi geometry. To reconstruct the exposure history of the meteoroid, Heymann et al. investigated several fragments recovered from known geographic locations around the crater for their shock features and cosmogenic nobel gases. They applied the Signer-Nier noble gas production rate model to establish the preatmospheric depth of the specimens in the meteoroid. Cosmic ray exposure ages suggested a multi-episodic irradiation, with 170 or 540 Ma being inferred for most of the samples studied while two anomalous specimens indicated a possible third exposure age at 940 Ma. Be-10 and Cl-36 have been measured in a number of these same samples by accelerator mass spectrometry (AMS), with use being made of the preatmospheric depths determined in Heymann et al. to construct production profiles. The present study extends the cosmogenic radionuclide data to Al-26 and compares the results with both the production rate model of Reedy and Arnold and production rates determined from the cross sections used by the Reedy-Arnold model (for the major nuclear reactions making Al-26) in combination with differential fluxes calculated using the Los Alamos High Energy Transport (LAHET) Code System. Model calculations for Be-10 and Cl-36 have also been obtained.

Michlovich, E.↗
NASA NTRS1994

Experimental study of lunar and SNC (Mars) magmas

The overall objectives of this research were to evaluate the role of C-O-S-Cl degassing processes in explaining vesiculation, oxidation state and fire-fountaining of lunar magmas by analysis of individual lunar glass spherules, and by experimental determination of equilibrium abundances and diffusion rates of C, S and Cl melt species in lunar glass compositions; and to determine possible primitive SNC magma compositions and the mineralogy of the mantle from which they were derived, and to evaluate P, T, XH2O etc. conditions at which they crystallize to form the SNC meteorites. After funding for one year, a project on the A15 volcanic green glass has been completed to the point of writing a first manuscript. Carbon-oxygen species C-O and CO2 are below detection limits (20 ppm) in these glasses, but there is up to 500 ppm S with concentrations both increasing and decreasing toward the spherule margins. Calculations and modeling indicate that C species could have been present in the volcanic gases, however. In a second project, experiments with low PH2O have resulted in refined estimates of the early intercumulus melt composition in the Chassigny meteorite which is generally accepted as a sample from Mars.

Rutherford, Malcolm J.↗
NASA NTRS1994

A change of upper cloud structure in Jupiter's South Equatorial Belt during the 1989-1990 event

We have analyzed two data sets of Jupiter's limb darkening taken before (March 1990) and after (March 1991) a South Equatorial Belt (SEB) disturbance. The vertical aerosol structure has been determined for the SEB, the Equatorial Zone (EZ), and the North Equatorial Belt (NEB). We find that all regions can be well represented with a two-cloud layer model, with slightly higher NH3-cloud top altitude in the EZ than in the two belts. The cloud single-scattering albedos tilda-omega(sub cl) (determined within plus or minus 0.003) show little difference in the EZ (from 0.9956 to 0.9952) and the NEB (from 0.9925 to 0.9926) during a 1-year period, while a relatively larger decrease is found in the SEB from 0.9975 to 0.9957, indicating the recovery of the belt through the disturbance. The NH3-cloud top altitude in the SEB shows the most prominent change, lower in 1990 and higher in 1991. We suggest that the brightening and the darkening of the SEB may originate not only from the changes of tilda-omega(sub cl) but also from changes of the ammonia condensation level in the atmosphere, probably due to a decrease of the tropospheric temperature and/or an increase of the ammonia vapor.

Satoh, Takehiko↗
NASA NTRS1982

Matrix isolation infrared spectra of hydrogen halide and halogen complexes with nitrosyl halides

Matrix isolation infrared spectra of nitrosyl halide (XNO) complexes with HX and X2 (X = Cl, Br) are presented. The relative frequency shifts of the HX mode are modest (ClNO H-Cl, delta-nu/nu = -0.045; BrNO H-Br, delta-nu/nu = -0.026), indicating weak hydrogen bonds 1-3 kcal/mol. These shifts are accompanied by significant shifts to higher frequencies in the XN-O stretching mode (CIN-O HCl, delta-nu/nu = +0.016; BrN-O HBr, delta-nu/nu = +0.011). Similar shifts were observed for the XN-O X2 complexes (ClN-O Cl2, delta-nu/nu = +0.009; BrN-O-Br2, delta-nu/nu = +0.013). In all four complexes, the X-NO stretching mode relative shift is opposite in sign and about 1.6 times that of the NO stretching mode. These four complexes are considered to be similar in structure and charge distribution. The XN-O frequency shift suggests that complex formation is accompanied by charge withdrawal from the NO bond ranging from about .04 to .07 electron charges. The HX and X2 molecules act as electron acceptors, drawing electrons out of the antibonding orbital of NO and strengthening the XN-O bond. The implications of the pattern of vibrational shifts concerning the structure of the complexes are discussed.

Allamandola, Louis J.↗
NASA NTRS1994

A measurement of the medium-scale anisotropy in the cosmic microwave background radiation

Observations from the first flight of the Medium Scale Anisotropy Measurement (MSAM) are analyzed to place limits on Gaussian fluctuations in the cosmic microwave background radiation (CMBR). This instrument chops a 30 min beam in a three-position pattern with a throw of +/- 40 min; the resulting data is analyzed in statistically independent single- and double-difference sets. We observe in four spectral channels at 5.6, 9.0, 16.5, and 22.5/cm, allowing the separation of interstellar dust emission from CMBR fluctuations. The dust component is correlated with the IRAS 100 micron map. The CMBR component has two regions where the signature of an unresolved source is seen. Rejecting these two source regions, we obtain a detection of fluctuations which match CMBR in our spectral bands of 0.6 x 10(exp -5) is less than Delta (T)/T is less than 2.2 x 10(exp -5) (90% CL interval) for total rms Gaussian fluctuations with correlation angle 0.5 deg, using the single-difference demodulation. Fore the double difference demodulation, the result is 1.1 x 10(exp -5) is less than Delta(T)/T is less than 3.1 x 10(exp -5) (90% CL interval) at a correlation angle of 0.3 deg.

Cheng, E. S.↗
NASA NTRS1994

Cosmic temperature fluctuations from two years of COBE differential microwave radiometers observations

The first two years of Cosmic Background Explorer (COBE) Differential Microwave Radiometers (DMR) observations of the cosmic microwave background (CMB) anisotropy are analyzed and compared with our previously published first year results. The results are consistent, but the addition of the second year of data increases the precision and accuracy detected CMB temperature fluctuations. The 2 yr 53 GHz data are characterized by rms temperature fluctuations of (delta-T)(sub rms) (7 deg) = 44 +/- 7 micro-K and (delta-T)(sub rms) (10 deg) = 30.5 +/- 2.7 micro-K at 7 deg and 10 deg angular resolution, respectively. The 53 x 90 GHz cross-correlation amplitude at zero lag is C(0)(sup 1/2) = 36 +/- 5 micro-K (68% CL) for the unsmoothed (7 deg resolution) DMR data. We perform a likelihood analysis of the cross-correlation function, with Monte Carlo simulations to infer biases of the method, for a power-law model of initial density fluctuations, P(k) proportional to R(exp n). The Monte Carlo simulations indicate that derived estimates of n are biased by +0.11 +/- 0.01, while the subset of simulations with a low quadrupole (as observed) indicate a bias of +0.31+/- 0.04. Derived values for 68% confidence intervals are given corrected (and not corrected) for our estimated biases. Including the quadrupole anisotropy, the most likely quadrupole-normalized amplitude is Q(sub rms-PS) = 14.3(sup + 5.2 sub -3.3) micro-K (12.8(sup + 5.2 sub -3.3) micro-K0 with a spectral index n = 1.42(sup + 0.49 sub -0.55)(n = 1.53(sup + 0.49 sub -0.55). With n fixed to 1.0 the most likely amplitude is 18.2 +/- 11.5 micro-K (17.4 +/- 1.5 micro-K). The marginal likelihood of n is 1.42 +/- 0.37 (1.53 +/- 0.37). Excluding the quadrupole anisotropy, the most likely quadrupole-normalized amplitude is Q(sub rms-PS) = 17.4(sup + 7.5 sub -5.2) micro-K (15.8(sup + 7.5 sub -5.2) micro-K) with a spectral index n = 1.11(sup + 0.60 sub -0.55) (n = 1.22(sup + 0.60 sub -0.55). With n fixed to 1.0 the most likely amplitude is 18.6 +/- 1.6 micro-K (18.2 +/- 1.6 micro-K). The marginal likelihood of n is 1.11 +/- 0.40 (1.22 +/- 0.40). Our best estimate of the dipole from the 2 yr DMR data is 3.363 +/- 0.024 mK toward Galactic coordinates (l, b) = (264.4 deg +/- 0.2 deg, 48.1 deg +/- 0.4 deg), and our best estimate of the rms quadrupole amplitude in our sky is 6 +/- 3 micro-K (68% CL).

Bennett, C. L.↗
NASA NTRS1994

Effects of heavy-element settling on solar neutrino fluxes and interior structure

We consider the effects of gravitational settling of both He and heavier elements on the predicted solar neutrino fluxes and interior sound speed and density profiles. We find that while the structural changes that result from the inclusion of both He and heavy-element settling are only slightly larger than the changes resulting from the inclusion of He settling alone, the additional increases in expected neutrino fluxes are of comparable size. Our preferred model with both He and heavy-element settling has neutrino count rates of 9.0 SNU for Cl-37 detectors and 137 SNU for Ga-71 detectors, as compared to 7.1 and 127 SNU for a comparable model without any diffusive separation, or 8.0 and 132 SNU for a model that includes He settling alone. We suggest that the correction factors by which the predicted neutrino fluxes of solar models calculated without including the effects of diffusion should be multiplied are 1.25 +/- 0.08 for Cl detectors, 1.07 +/- 0.02 for Ga detectors, and 1.28 +/- 0.09 for the B-8 flux (1 sigma errors). Comparison of internal sound speed and density profiles strongly suggests that the additional changes in calculated p-mode oscillation frequencies due to the inclusion of heavy-element settling will be small compared to the changes that result from He settling alone, especially for the higher degree modes. All models with diffusive separation give much better agreement with the observed depth of the convection zone than do nondiffusive models. The model that includes both He and heavy-element settling requires an initial He mass fraction Y = 0.280 and has a surface He abundance of Y = 0.251 at the solar age.

Proffitt, Charles R.↗
NASA NTRS1995

Non-LTE line-blanketed model atmospheres of hot stars. 1: Hybrid complete linearization/accelerated lambda iteration method

A new munerical method for computing non-Local Thermodynamic Equilibrium (non-LTE) model stellar atmospheres is presented. The method, called the hybird complete linearization/accelerated lambda iretation (CL/ALI) method, combines advantages of both its constituents. Its rate of convergence is virtually as high as for the standard CL method, while the computer time per iteration is almost as low as for the standard ALI method. The method is formulated as the standard complete lineariation, the only difference being that the radiation intensity at selected frequency points is not explicity linearized; instead, it is treated by means of the ALI approach. The scheme offers a wide spectrum of options, ranging from the full CL to the full ALI method. We deonstrate that the method works optimally if the majority of frequency points are treated in the ALI mode, while the radiation intensity at a few (typically two to 30) frequency points is explicity linearized. We show how this method can be applied to calculate metal line-blanketed non-LTE model atmospheres, by using the idea of 'superlevels' and 'superlines' introduced originally by Anderson (1989). We calculate several illustrative models taking into accont several tens of thosands of lines of Fe III to Fe IV and show that the hybrid CL/ALI method provides a robust method for calculating non-LTE line-blanketed model atmospheres for a wide range of stellar parameters. The results for individual stellar types will be presented in subsequent papers in this series.

Hubeny, I.↗
NASA NTRS1994

The response of C1O radical concentrations to variations in NO2 radical concentrations in the lower stratosphere

The respose of ClO concentrations to changes in NO2 concentrations has been inferred from simultaneous observations of (ClO), (NO), (NO2) and (O3) in the midlatitude lower stratosphere. This analysis demonstrates that (ClO) is inversely correlated with (NO2), consistent with formation and photolysis of (ClONO2). A factor of ten range in the concentration if NO2 was sampled (0.1 to 1 x 10(exp 9) mol/cu cm), with a comparable range in the ratio of (ClO) to total available inorganic chlorine (1% less than or equal to (ClO)/(Cl(sub y)) less than or equal to 5%. This analysis leads to an estimate of (ClONO2)/(Cl(sub y)) = 0.12 (x/2), in the mid-latitude, lower-stratospheric air masses sampled.

Stimfle, R. M.↗
NASA NTRS1993

Two chondrule groups each with distinctive rims in Murchison recognized by cathodoluminescence

Two groups of chondrules in the Murchison CM chondrite, which have previously been identified on the basis of FeO in the chondrule grains, are readily identified from cathodoluminescence (CL) and belong to those of the ordinary chondrite group A and B chondrules of Sears et al. (1992a). All chondrules are surrounded by fine-grained rims containing forsterite with bright red CL, but on group A chondrules an outer thin rim grades into a much thicker rim, with a lower density of forsterite grains, which in turn grades into the central chondrule. Group B chondrules have only the thin outer rim with a high density of small forsterite grains. This is the first time an unequivocal correlation has been observed between chondrule rim thickness and the composition of the object on which the rim is located. We suggest that while all objects in the meteorite (group B chondrules, refractory inclusions, mineral and chondrule fragments, clasts) acquired a very thin rim during processing in a wet regolith, the thick rims on group A chondrules were formed by aqueous alteration of precursor metal- and sulfide-rich rims which are a characteristic of group A chondrules in ordinary chondrites.

Sears, Derek W. G.↗
NASA NTRS1996

Ozone Production and Loss Rate Measurements in the Middle Stratosphere

The first simultaneous measurements of HO(x), NO(x), and Cl(x) radicals in the middle stratosphere show that NO(x) catalytic cycles dominate loss of ozone (O3) for altitudes between 24 and 38 km; Cl(x) catalytic cycles are measured to be less effective than previously expected; and there is no 'ozone deficit' in the photochemically dominated altitude range from 31 and 38 km, contrary to some previous theoretical studies.

Jucks, Kenneth W.↗
NASA NTRS1997

New Approaches to Waterproofing of Space Shuttle Insulating Materials

Future reusable space vehicles will be in service much more frequently than current space shuttles. Therefore, rapid reconditioning of spacecraft will be required. Currently, the waterproofing of space shuttles after each re-entry takes 72 hours and requires substantial labor. In addition, the currently used waterproofing reagent, DiMethylEthoxySilane (DMES), is considered toxic, and ethanol fumes are released during its hydrolytic activation. Consequently, a long time period, which is not acceptable for future operations, is needed to ensure that 0 the excess volatile compounds are removed before further maintenance of the space vehicle can be performed. The objective of this project was to assist NASA Ames in finding improved waterproofing systems by identifying suitable waterproofing agents that can be applied by vapor phase deposition and will be less toxic, bond more rapidly to the insulation material surface, and potentially have higher thermal stability than the DMES system. Several approaches to achieve faster waterproofing with less toxicity were assessed using the following alternatives: Reactive volatile compounds that are rapidly deposited by chemical bonding at the surface and leave no toxic volatiles. Reactive reagents that are the least toxic. Nonvolatile reagents that are very reactive and bond strongly to the insulating material surface. Three specific types of potential reagents were chosen for evaluation in this project: 1. Volatile reagents with Si-Cl functional groups for vapor deposition 2. Volatile reagents with Si-H functional groups for vapor deposition 3. Nonvolatile oligomeric or polymeric reactive siloxanes that are assumed to have higher thermal stability and/or strong bonding to the insulating material. The chemistry involved in the project was targeted at the generation of intermediates having reactive Si-OH bonds for the formation of either volatile species or polymeric species that bond rapidly to the surface and also cure rapidly. We focused on two chemical reactions@-hydrolysis of Si-Cl bonds and catalytic dehydrocoupling of Si-H bonds.

Blum, Yigal D.↗
NASA NTRS1992

Purification and Properties of an ATPase from Sulfolobus solfataricus

A sulfite-activated ATPase isolated from Sulfolobus solfataricus had a relative molecular mass of 370,000. It was composed of three subunits whose relative molecular masses were 63,000, 48,000, and 24,000. The enzyme was inhibited by the vacuolar ATPase inhibitors nitrate and N-ethylmaleimide; 4-chloro-7-nitrobenzo-furazan (NBD-Cl) was also inhibitory. N-Ethylmaleimide was predominately bound to the largest subunit while NBD-CL was bound to both subunits. ATPase activity was inhibited by low concentrations of p-chloromercuri-phenyl sulfonate and the inhibition was reversed by cysteine which suggested that thiol groups were essential for activity. While the ATPase from S. solfataricus shared several properties with the ATPase from S. acidocaldarius there were significant differences. The latter enzyme was activated by sulfate and chloride and was unaffected by N-ethylmaleimide, whereas the S. solfataricus ATPase was inhibited by these anions as well as N-ethyimaleimide. These differences as well as differences that occur in other vacuolar-like ATPases isolated from the methanogenic and the extremely halophilic bacteria suggest the existence of several types of archaeal ATPases, none of which have been demonstrated to synthesize ATP.

Hochstein, Lawrence I.↗
NASA NTRS1995

Accurate ab Initio Quartic Force Fields, Vibrational Frequencies, and Heats of Formation for FCN, FNC, ClCN, and ClNC

The XCN and XNC (X = F, Cl) isomers have been investigated using the CCSD(T) method in conjunction with correlation consistent basis sets. Equilibrium geometries, harmonic frequencies, anharmonic constants, fundamental frequencies, and heats of formation have been evaluated. Agreement with experiment for the fundamental frequencies is very good, even for nu(sub 2), for CICN, which is subject to a strong Fermi resonance with 2nu(sub 3). It is also shown that a second-order perturbation theory approach to solving the nuclear Schroedinger equation gives results in excellent agreement with essentially exact variational calculations. This is true even for nu(sub 2) of ClCN, provided that near-singular terms are eliminated from the perturbation theory formulas and the appropriate Fermi interaction energy matrix is then diagonalized. A band at 615/cm, tentatively assigned as the Cl-N stretch in ClNC in matrix isolation experiments, is shown not to be due to ClNC. Accurate atomization energies are determined and are used to evaluate accurate heats of formation (3.1 +/- 1.5, 33.2 +/- 1.5, 72.6 +/- 1.5, and 75.9 +/- 1.5 kcal/mol for FCN, ClCN, FNC, and ClNC, respectively). It is expected that the theoretical heats of formation for FCN, FNC, and ClNC are the most accurate available.

Lee, Timothy J.↗
NASA NTRS1996

Pressure-Dependent Yields and Product Branching Ratios in the Broadband Photolysis of Chlorine Nitrate

The photolysis of chlorine nitrate was studied using broadband flash photolysis coupled with long-path ultraviolet-visible absorption spectroscopy. Branching ratios for the Cl + NO3 and ClO + NO2 product channels were determined from time-dependent measurements of ClO and NO3 concentrations. Yields of the ClO and NO3 products displayed a dependence on the bath gas density and the spectral distribution of the photolysis pulse. Product yields decreased with increasing bath gas density regardless of the spectral distribution of the photolysis pulse; however, the decrease in product yield was much more pronounced when photolysis was limited to longer wavelengths. For photolysis in a quartz cell (lambda > 200 nm) the yield decreased by a factor of 2 over the pressure 10-100 Torr. In a Pyrex cell (lambda > 300 nm), the yield decreased by a factor of 50 over the same pressure range. When photolysis was limited to lambda > 350 nm, the yield decreased by a factor of 250. Branching ratios for the photolysis channels [ClONO2 + h.nu yields ClO + NO2 (1a) and ClONO2 + h.nu yields Cl + NO3 (lb)] were determined from the relative ClO and NO3 product yields at various pressures. Although the absolute product yield displayed a pressure dependence, the branching between the two channels was independent of pressure. The relative branching ratios (assuming negligible contributions from other channels) are 0.61 +/- 0.20 for channel 1a and 0.39 +/- 0.20 for channel lb for photolysis with lambda > 200 nm and 0.44 +/- 0.08 for channel 1a and 0.56 +/- 0.08 for channel 1b for photolysis with lambda > 300 nm. The implications of these results for the chemistry of the lower stratosphere are discussed.

Nickolaisen, Scott L.↗
NASA NTRS1999

Calculations of Polar Ozone Loss Rates

We calculate vortex-averaged ozone loss rates at 465-K potential temperature during the Aug.-Sept. time period in the southern hemisphere and Feb.-Mar. time period in the northern hemisphere. Ozone loss rates are calculated two ways. First, from the time series of measurements of 03. Second, from measurements of ClO, from which ozone loss is inferred based on our theories of Cl-catalyzed ozone destruction. Both measurement sets are from the Upper Atmosphere Research Satellite (UARS) Microwave Limb Sounder (MLS) instrument. We find good agreement between vortex-averaged ozone loss rates calculated from these methods. Our analysis provides no support for recent work suggesting that current theories of Cl-catalyzed ozone loss underestimate the observed decrease in polar ozone during the ozone "hole" period.

Dessler, A. E.↗
NASA NTRS1999

The Budget and Partitioning of Stratospheric Chlorine During the 1997 Arctic Summer

Volume mixing ratio profiles of HCl, HOCl, ClNO3, CH3Cl, CFC-12, and CFC-11, CCl4, HCFC-22, and CFC-113 were measured simultaneously from 9 to 38 km by the Jet Propulsion Laboratory MkIV Fourier Transform Infrared solar absorption spectrometer during two balloon flights from Fairbanks, Alaska (64.8 N), on May 8 and July 8, 1997. The altitude variation of total organic chlorine (CCl(sub y)), total inorganic chlorine (Cl(sub y)), and the nearly constant value (3.7 +/- 0.2 ppbv) of their sum (Cl(sub TOT)) demonstrates that the stratospheric chlorine species available to react with O3 are supplied by the decomposition of organic chlorinated compounds whose abundances are well quantified. Measured profiles of HCl and ClNO3 agree well with profiles found by photochemical model (differences < 10% for altitudes below 35 km) constrained by various other constituents measured by MkIV. The production of HCl by ClO + OH plays a relatively small role in the partitioning of HCl and ClNO3 for the sampled air masses. However, better agreement with the measured profiles of HCl and ClNO3 is obtained when this source of HCl is included in the model. Both the measured and calculated [ClNO3]/[HCl] ratios exhibit the expected near linear variation with [O3](sup 2)/[CH4] over a broad range of altitudes. MkIV measurements of HCl, ClNO3, and CCl(sub y) agree well with ER-2 in situ observations of these quantities for directly comparable air masses. These results demonstrate good understanding of the budget of stratospheric chlorine and that the partitioning of inorganic chlorine is accurately described by photochemical models that employ JPL97 reaction rates and production of HCl from ClO + OH for the environmental conditions encountered: relatively warm temperatures, long periods of solar illumination, and relatively low aerosol surface areas.

Sen, B.↗