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At least 37 records · Page 2

Asymptotic Energies and QED Shifts for Rydberg States of Helium

This paper reviews progress that has been made in obtaining essentially exact solutions to the nonrelativistic three-body problem for helium by a combination of variational and asymptotic expansion methods. The calculation of relativistic and quantum electrodynamic corrections by perturbation theory is discussed, and in particular, methods for the accurate calculation of the Bethe logarithm part of the electron self energy are presented. As an example, the results are applied to the calculation of isotope shifts for the short-lived 'halo' nucleus He-6 relative to He-4 in order to determine the nuclear charge radius of He-6 from high precision spectroscopic measurements carried out at the Argonne National Laboratory. The results demonstrate that the high precision that is now available from atomic theory is creating new opportunities to create novel measurement tools, and helium, along with hydrogen, can be regarded as a fundamental atomic system whose spectrum is well understood for all practical purposes.

Drake, G.W.F.↗

Ecosystem Impacts of Woody Encroachment In Texas: A Spatial Analysis Using AVIRIS

Woody encroachment, the increase of woody plant density relative to herbaceous vegetation, has been documented in drylands of Texas as well as worldwide (Archer 1994, Harrington and Harman 1995, Moleele et al. 2002). Over-grazing, fire suppression and climate change are implicated in the shift from open grasslands to ecosystems now populated by trees and shrubs (Scholes and Archer 1997, Archer et al. 2001), such as Prosopis glandulosa var. glandulosa (honey mesquite) in north Texas (Teague et al. 1997, Ansley et al. 2001, Asner et al. 2003a). Several studies have examined changes in ecosystem properties accompanying woody vegetation encroachment in the Southwest U.S., with research focused on increases in plant and soil carbon (C) and nitrogen (N) stores (Hoffman and Jackson 2000, Asner et al. 2003a), isotopic shifts in these pools (Boutton 1999, Archer et al. 2001), and increases in N cycling rates (Rundel et al. 1982, Hibbard et al. 2001). However, little is known regarding the impact of woody encroachment on N trace gas emissions from dryland regions such as Texas. NOx is produced in the soil during the processes of nitrification and denitrification (Firestone and Davidson 1989). The total N efflux from soils is most directly influenced by the internal cycling of N, which at a regionalscale, is controlled by the inputs and availability of N from vegetation via litterfall and subsequent decomposition (Robertson et al. 1989). Although plot-scale studies are critical to understanding controls over N oxide emissions, regionalization of the measurements is impeded by spatial variation in the factors contributing most to N cycling processes: soil properties (affecting soil moisture regimes and N stocks) and vegetation cover (affecting litter inputs and N uptake). While broad patterns in ecosystem structure and vegetation composition co-vary with general patterns of trace gas emissions (Matson 1997), there is no easily measured index of N availability that can be applied for regional-scale studies of N oxide fluxes. Remote sensing is arguably the only approach available to develop a spatially-explicit understanding of ecosystem processes. More specifically, remotely detectable spatial patterns in the distal controls over soil N properties, such as vegetation cover, land use and soil type (Robertson et al. 1989), should be exploited for regional studies of N oxide emissions. The woody encroachment phenomenon provides an opportunity to test the strength of the relationship between N oxide emissions and those factors controlling the fluxes that can be remotely measured. If such linkages can be firmly established, and if the spatial pattern of distal controls is relevant, then the combination of field measurements and remote sensing offers to improve regional-scale N oxide estimates. The paper presents the utility of linking field based sampling of soil NOx emissions with very high resolution remote sensing estimates of woody vegetation cover from the NASA AVIRIS, Airborne Visible-Infrared Imaging Spectrometer (Green et al. 1998, Asner and Green 2001) and automated spectral mixture analysis (Asner and Lobell 2000, Asner and Heidebrecht 2002) that provide a means to spatially extrapolate soil NOx emissions to the regional scale.

Martin, Roberta E.↗

Structures of aspartic acid-96 in the L and N intermediates of bacteriorhodopsin: analysis by Fourier transform infrared spectroscopy

The light-induced difference Fourier transform infrared spectrum between the L or N intermediate minus light-adapted bacteriorhodopsin (BR) was measured in order to examine the protonated states and the changes in the interactions of carboxylic acids of Asp-96 and Asp-115 in these intermediates. Vibrational bands due to the protonated and unprotonated carboxylic acid were identified by isotope shift and band depletion upon substitution of Asp-96 or -115 by asparagine. While the signal due to the deprotonation of Asp-96 was clearly observed in the N intermediate, this residue remained protonated in L. Asp-115 was partially deprotonated in L. The C = O stretching vibration of protonated Asp-96 of L showed almost no shift upon 2H2O substitution, in contrast to the corresponding band of Asp-96 or Asp-115 of BR, which shifted by 9-12 cm-1 under the same conditions. In the model system of acetic acid in organic solvents, such an absence of the shift of the C = O stretching vibration of the protonated carboxylic acid upon 2H2O substitution was seen only when the O-H of acetic acid is hydrogen-bonded. The non-hydrogen-bonded monomer showed the 2H2O-dependent shift. Thus, the O-H bond of Asp-96 enters into hydrogen bonding upon conversion of BR to L. Its increased hydrogen bonding in L is consistent with the observed downshift of the O-H stretching vibration of the carboxylic acid of Asp-96.

NASA Discipline Exobiology↗

Depositional facies and aqueous-solid geochemistry of travertine-depositing hot springs (Angel Terrace, Mammoth Hot Springs, Yellowstone National Park, U.S.A.)

Petrographic and geochemical analyses of travertine-depositing hot springs at Angel Terrace, Mammoth Hot Springs, Yellowstone National Park, have been used to define five depositional facies along the spring drainage system. Spring waters are expelled in the vent facies at 71 to 73 degrees C and precipitate mounded travertine composed of aragonite needle botryoids. The apron and channel facies (43-72 degrees C) is floored by hollow tubes composed of aragonite needle botryoids that encrust sulfide-oxidizing Aquificales bacteria. The travertine of the pond facies (30-62 degrees C) varies in composition from aragonite needle shrubs formed at higher temperatures to ridged networks of calcite and aragonite at lower temperatures. Calcite "ice sheets", calcified bubbles, and aggregates of aragonite needles ("fuzzy dumbbells") precipitate at the air-water interface and settle to pond floors. The proximal-slope facies (28-54 degrees C), which forms the margins of terracette pools, is composed of arcuate aragonite needle shrubs that create small microterracettes on the steep slope face. Finally, the distal-slope facies (28-30 degrees C) is composed of calcite spherules and calcite "feather" crystals. Despite the presence of abundant microbial mat communities and their observed role in providing substrates for mineralization, the compositions of spring-water and travertine predominantly reflect abiotic physical and chemical processes. Vigorous CO2 degassing causes a +2 unit increase in spring water pH, as well as Rayleigh-type covariations between the concentration of dissolved inorganic carbon and corresponding delta 13C. Travertine delta 13C and delta 18O are nearly equivalent to aragonite and calcite equilibrium values calculated from spring water in the higher-temperature (approximately 50-73 degrees C) depositional facies. Conversely, travertine precipitating in the lower-temperature (< approximately 50 degrees C) depositional facies exhibits delta 13C and delta 18O values that are as much as 4% less than predicted equilibrium values. This isotopic shift may record microbial respiration as well as downstream transport of travertine crystals. Despite the production of H2S and the abundance of sulfide oxidizing microbes, preliminary delta 34S data do not uniquely define the microbial metabolic pathways present in the spring system. This suggests that the high extent of CO2 degassing and large open-system solute reservoir in these thermal systems overwhelm biological controls on travertine crystal chemistry.

Non-NASA Center↗

Vibrational spectra and structure of azomethane and azomethane-d6.

The infrared and Raman spectra of azomethane and azomethane-d(6) were examined in detail. Vibrational data provided definitive verification of a trans-structure with C(2h) symmetry. A vibrational assignment is proposed for the 24 fundamental modes based upon the observed contours, isotopic shift ratios, and group frequency correlations. Spectra of the polycrystalline samples indicate that there are at least four molecules per unit cell, since a number of the bands were observed to be split into doublets. The crystal also appeared to have a center of symmetry, since mutual exclusion was clearly operative.

Durig, J. R.↗

Titan's spectrum and atmospheric composition

Spectroscopic evidence shows that hydrogen atoms are major constituents of Titan's atmosphere. Anomalous enhancement of the methane absorption band is attributed to isotopic shifts arising from methane photolysis. Anomalous ultraviolet absorption features suggest high altitude dust and an elevated cloud layer overlaying most of the methane in the atmosphere.

Trafton, L. M.↗

Barium and neodymium isotopic anomalies in the Allende meteorite

The discovery of Ba and Nd isotopic anomalies in two inclusions from the Allende meteorite is reported. The inclusions are Ca-Al-rich objects typical of the type considered as high-temperature condensation products in the solar nebula and contain distinctive Mg and O isotopic anomalies of the FUN (mass Fractionation, Unknown Nuclear processes) type. Mass-spectrometry results are discussed which show that inclusion C1 has anomalies in Ba at masses 134 and 136, while inclusion EK1-4-1 exhibits large marked negative anomalies at 130, 132, 134, and 136, as well as a positive anomaly at 137. It is also found that inclusion EK1-4-1 shows marked negative anomalies in Nd at masses 142, 146, 148, and 150, in addition to a positive anomaly at 145. These isotopic shifts are attributed to addition of r-process nuclei rather than mass fractionation. It is suggested that an onion-shell supernova explosion followed by injection into the solar nebula is the most likely generic model that may explain the observations.

Mcculloch, M. T.↗

High-resolution infrared spectra of v sub 3 and 2v sub 3 of germane

Band origins, secondary (or satellite) lines, and intensity anomalies are discussed for the infrared spectra of v sub 3 and 2v sub 3 of germane. Germane has been tentatively identified as spectroscopically active in the atmosphere of Jupiter. The molecule is also of interest for studies of isotope shifts in spherical-top spectra such as those measured in methane at 6000 kaysers.

Daunt, S. J.↗

Al-26 from red giants

Simplified models of thermally pulsing red giants are investigated, with particular emphasis on predicting the extent to which nuclear processing at the base of the convective envelope in conjunction with processing in the thermally unstable He shell can synthesize Al-26 (tau/1/2/ = 7.2 x 10 to the 5th yr). Values of Al-26/Al-27 of about 0.5-1, with Al-27/Al-27(solar) of about 1-2, are predicted in some cases. It is pointed out that such results can lead to isotope shifts in the absorption lines of AlH and AlO, which should be observationally identifiable in some late-type supergiants. The possible connection with the anomalous Mg-26 content (assigned to the decay of Al-26) detected in some meteorites and the connection with formation of the solar system are also touched on.

Norgaard, H.↗

A line parameter list for the nu2 and nu4 bands of /C-12/H4 and /C-13/H4, extended to J-prime = 25 and its application to planetary atmospheres

Line parameters (transition frequencies, line strengths, line widths, ground state energies and quantum identifications) for the nu2 and nu4 bands of (C-12)H4 and (C-13)H4 have been calculated for J-prime equal to or less than 25 using the simultaneous coupled fitting procedure of Gray and Robiette. Molecular constants for the nu2 band of (C-13)H4 were estimated from isotopic shifts from (C-12)H4 values. Agreement with laboratory spectra, where available, is always well within 1 kayser over the entire spectral range covered by the list. The most serious problem in comparison with laboratory data is the omission of lines belonging to 'hot' bands in this spectral region. This list is valuable in remote sensing problems for sorting out lines of trace species from weak methane lines and for determining the atmospheric opacity in relatively transparent spectral regions. Applications of the parameter list are demonstrated for remote sounding of the Jovian atmosphere.

Orton, G. S.↗

New evidence from the South China Sea for an abrupt termination of the last glacial period

Results demonstrating an abrupt change in the rate and character of sedimentation in the South China Sea at the close of the last glacial period are presented. Radiocarbon dating and its position in the oxygen isotope shift suggest that this change may be coincident with the abrupt change in climatic conditions seen at high latitudes in the North Atlantic and the Antarctic at 13 kyr BP. These results support the contention that a major global climatic change occurred between 14 and 13 kyr BP.

Broecker, W. S.↗

Near-infrared absorption spectra of (O-16)3 and (O-18)3 - Adiabatic energy of the 1A2 state?

The band positions and isotope shifts for the weak vibronic bands of O3 near 1 micron are determined experimentally using a low-resolution dual-beam absorption spectrometer with a 0.2-m holographic-grating monochromator and identical absorption chambers of volume about 600 cu cm and optical path length 46 cm. The experimental setup and procedures and the signal-processing methods applied are described, and the results are presented in tables and graphs. It is found that the adiabatic energy of the 1A2 state lies 9990 + or - 70/cm (1.24 + or - 0.01 eV) above the electronic ground state, close to the O + O2 dissociation limit. The applicability of the present results to studies of O3 in the upper atmosphere is indicated.

Anderson, S. M.↗

Search for solar-type nitrogen in the gas-rich Pesyanoe meteorite

An initial study carried out to isolate and characterize solar wind N in the dark portion of the enstatite achondrite Pesyanoe is presented. Nitrogen isotopic data obtained from a stepwise gas release of two grain-size fractions of the gas-rich meteorite are given. It is determined that more than one trapped N component is present and that indigenous N is released above 1000 C with an isotopic signature of delta N-15 = -33 per mil. A heavy N component is detected at 700-800 C, and coincides with a major release of solar-type noble gases. A lower limit of delta N-15 = -6 per mil is defined by the isotopic shifts at this range of temperature for the second element of a two-component mixture, whereas the delta N-15 signature depends on the adopted elemental abundances for a solar-type component. It is pointed out that the timing of solar wind loading of Pesyanoe is only constrained to correspond to the cosmic ray exposure age (less than 60 Ma), although it is generally assumed that this irradiation took place during an early stage.

Murty, S. V. S.↗

Effect of isotopic substitution on the visible absorption spectrum of ozone

Gas-phase spectra for (O-16)3 and (O-18)3 are examined to consider the electronic states which cause the Chappuis bands. Specifications of the spectrometer and spectra calibrations are given. The results of both a conventional description of the vibrational structure and an examination of the autocorrelation functions are discussed. Transitions to two electronically excited states are the significant features of the isotope shifts. The transitions are characterized by adiabatic energies about 750/cm apart, and the higher energy approaches 16,400/cm. The vibrational structure of the higher state accompanies a relatively simple progression, and the lower state accompanies one isolated band. The autocorrelation analysis shows that for (O-16)3, major recurrences near 31 and 41 fs are found, and longer equivalent times are found for (O-18)3. At longer times, minor recurrences are also found. The results are considered significant for the understanding of the electronic and vibrational structures of the Chappuis bands. Suggestions for future work based on these results are discussed.

Anderson, Stuart M.↗

FONO - A difficult case for theory and experiment

High levels of ab initio theory are used to investigate the equilibrium structures, vibrational spectra, and relative energetics of FNO2, cis-FONO, and trans-FONO isomers. FNO2 is determined to be 36.9 +/- 2.5 kcal/mol (0 K) more stable than cis-FONO, which is more stable than trans-FONO by 2.5 +/- 1.0 kcal/mol (0 K). The molecular structure of cis-FONO is shown to have typical F-O and central O-N single bond distances, indicating that cis-FONO has a structure analogous to HONO. The computed vibrational spectrum of cis-FONO is shown to be consistent with IR matrix isolation experiments, including isotopic shifts. The experimentally deduced structure of FONO is shown to be incorrect because one of the vibrational bands included in the normal coordinate analysis is either a combination band or an overtone.

Lee, Timothy J.↗

The diatom record from beneath the West Antarctic Ice Sheet and the global proxy perspective

Recent glaciological evaluation and modeling of the marine-based West Antarctic Ice Sheet (WAIS) support the possibility that the WAIS disintegrated during one or more Pleistocene interglacial period(s). The magnitude of sea level and oxygen isotope variation during certain late-Pleistocene interglacial periods is also consistent with the possibility of major retreat of the WAIS. Although oxygen isotopes from deep-sea sediments provide the best available proxy record for global ice volume (despite the ambiguities in the record), the source of ice volume changes must be hypothesized. Based on the intensity of interglacial isotopic shifts recorded in Southern Ocean marine sedimentary records, stage 11 (400,000 years ago) is the strongest candidate for WAIS collapse, but the records for stages 9, 7, and 5.5 are all consistent with the possibility of multiple late-Pleistocene collapses. Seismic reflection studies through the WAIS have revealed thick successions of strata with seismic characteristics comparable to upper Tertiary marine sediments. Small samples of glacial diamictons from beneath the ice sheet have been collected via hot-water drilled access holes. These sediments include mixed diatom assemblages of varying ages. Late-Miocene diatoms dominate many samples, probably reflecting marine deposition in West Antarctic basins prior to development of a dominantly glacial phase in West Antarctica. In addition to late-Miocene diatoms, samples from Upstream B (1988/89) contain rare post-Miocene diatoms, many of which imply deposition in the West Antarctic interior during one or more Pleistocene deglaciation periods. Age-diagnostic fossils in glacial sediments beneath ice sheets provide relatively coarse chronostratigraphic control, but they do contain direct evidence of regional deglaciation. Thus, sub-glacial till samples provide the evidence regarding the source of ice sheet variability seen in well-dated proxy records. Combined, these independent data sets can provide a more comprehensive and less speculative interpretation of the history of past glacial minima in currently glaciated polar regions.

Scherer, Reed P.↗

Mg and Ti isotopes in presolar Al2O3

Oxygen isotopic compositions and initial Al-26/Al-27 ratios were reported for two presolar Al2O3 grains, Orgueil B and Bishunpur B39. In Orgueil B, O-17/O-16 is about twice the solar value but O-18/O-16 is normal. In B39, O-17/O-16 is approximately 7x higher than solar and O-18/O-16 is 0.6x the solar value. Spectroscopic observations of red giant stars show similar O compositions, which result when material that has experienced partial H burning is mixed into the stellar envelope by the first dredge-up. The O-17/O-16 ratios indicate that Orgueil B originated around a star of approximately 1.5 solar mass, while B39 formed around either a approximately 2 solar mass or 4-7 solar mass star. Both grains formed with Al-26/Al-27 ratios of approximately 10(exp -3). Aluminum-26 is produced in the H shell after core H burning has ceased and first dredge-up has occurred. It is spread through the envelope by the third dredge-up, which occurs in low- and intermediate-mass stars as a series of mixing events driven by thermal pulses in the He shell. In intermediate-mass stars (3-8 solar mass), Al-26 can also be brought to the surface by the second dredge-up, which occurs at the end of core He burning. We have measured Ti isotopes by ion probe in Orgueil B and Bishunpur B39, looking for evidence of He-shell nucleosynthesis. Stars of approximately 1.5 solar mass do not experience second dredge-up, so the Al-26 in Orgueil B must have been mixed outward during third dredge-up, which also supplies He-shell material to the envelope. The size of the isotopic shifts in Ti and Mg suggest that Orgueil B contains approximately 5-10x more material from the He-shell than from the H-shell. In contrast, the lack of measurable Mg and Ti anomalies in B39 imply little or no He-shell contribution. This indicates that Al-26 in B39 was supplied by second dredge-up prior to He-shell ignition and points to a parent star of 4-7 solar mass.

Huss, G. R.↗

H, C, N, and O Isotopic Substitution Studies of the 2165 cm (4.62 micron) "XCN" Feature Produced by UV Photolysis of Mixed Molecular Ices

To better understand the chemical species that gives rise to the 2165/cm (4.62 micron) "XCN" absorption feature seen towards embedded protostars such as W33A, we have performed laboratory studies using deuterium (H-2) isotopic labeling. We report the observation of a small but significant deuterium isotope shift for the "XCN" peak which demonstrates that the atomic motion(s) causing the "XCN" band in the laboratory samples must involve hydrogen. We also report the results of C-13, N-15 and O-18 labeling experiments that are consistent with previously reported values.

Bernstein, Max P.↗