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At least 865 records · Page 48

The Submillimeter Wave Spectrum of Isotopic Methyl Cyanide

The laboratory submillimeter wave rotational spectrum of the 13CH3CN, CH3C13CN, and CH3C15N isotopomers of methyl cyanide has been observed in natural abundance in the 294 to 607 GHz region. The maximum J and K values are 34 and 14, respectively. Fifteen additional CH3CN transitions up to K = 21 were also measured. The transitions of all four species are fitted to a symmetric top Hamiltonian, and the rotation and distortion constants are determined. The 14N quadrupole and spin rotation coupling constants are also calculated and presented. Suggested values for many other parameters, which could not be directly determined from the isotope spectra, are calculated from the normal species values and isotope relationships. The determined and calculated constants should predict the spectrum of the three isotopomers to well over 1 THz accurately enough for astronomical assignments.

Pearson, J. C.↗

Methanol and hydrogen sulfide in comet P/Halley

The Neutral Mass Spectrometer on the Giotto spacecraft measured the gas and ion composition in the coma of comet P/Halley. A detailed model of the ion chemistry inside the contact surface located at 4660 km is used to interpret the measured ion desnity profiles in the 32 to 35 amu/e mass range. The masses 33 and 35 amu/e are dominated by the protonated methanol and hydrogen sulfide ions CH3OH2(+) and H3S(+). Both profiles are essentially compatible with CH3OH and H2S originating from the nucleus only. The production rates relative to water are Y(CH3OH) = Q(CH3OH)/Q(H2O) = 1.7% and Y(H2S) = 0.41%. Our Y(CH3OH) agrees well with a determination from IR spectra obtained about 6 weeks after the Giotto encounter with P/Halley. In 7 other comets IR and microwave observations give Y(CH3OH) values between about 0.7 and 6%, indicating that the methanol abundance shows a strong variability from comet to comet. In three other comets Y(H2S) values between 0.2 and 0.5% have been reported. In addition to H2S(+), only ions containing minor isotopes of H, C, O and S contribute to mass 34 amu/e (e.g. (34)S(+), (13)CH3OH2(+), CH4DO(+)). These contributions can be calculated from the measured densities of the ions containing the major isotopes and the H2S(+) contribution from the measured H3S(+) density. From mass 34 amu/e we can also derive an upper limit of 1% for the abundance of deuterated methanol. This limit is at most marginally compatible with a direct interstellar origin of the CH3OH in P/Halley as the measured interstellar abundance of deuterated methanol is 1 to 6%.

Eberhardt, P.↗

Precision Mass Measurements Reveal Low Neutron Pairing in Tin beyond 𝑁=82 and Its Impact on Stellar Nucleosynthesis

We present a study on neutron-rich tin (𝑍 =50) isotopes beyond the doubly closed shell of 𝑁 = 82 through high-precision mass measurements, including the first-ever measurements of the masses of 136 Sn, 137 Sn, and 138 Sn isotopes. These measurements enhance our understanding of the nuclear structure and astrophysical nucleosynthesis in this previously unexplored region. The new mass data are used for evaluation of the final abundances of mass numbers 𝐴 =135 and 137 in 𝑟-process network calculations. Our findings reveal a notable change in the empirical pairing gap for tin isotopes beyond the 𝑁 = 82 closed shell and a shift in the two-neutron-separation energy slope compared to heavier elements above the shell closure. A new set of ab initio calculations effectively describes these observed trends.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Nanoscale wetting controls reactive Pd ensembles in synthesis of dilute PdAu alloy catalysts

The performance of bimetallic dilute alloy catalysts is largely determined by the size of minority metal ensembles on the nanoparticle surface. By analyzing the synthesis of catalysts comprising Pd 8 Au 92 nanoparticles supported on silica using surface-sensitive techniques, we report that whether Pd overgrowth occurs before or after Au nanoparticle deposition onto the support controls the surface Pd ensemble size and abundance. These differences in Pd ensembles influence catalytic reactivity in H 2 –D 2 isotope exchange and benzaldehyde hydrogenation, which, in correlation with theoretical calculations, is used to elucidate the active site(s) in each reaction. To clarify how the synthetic sequence controls the formation of Pd ensembles, we combine numerical wetting calculations and molecular dynamics simulations (with a machine-learned force field) to visualize Pd deposition and migration on the nanoparticle surface, respectively. Our results suggest that the nanoparticle–support interface restricts nanoparticle accessibility to Pd deposition, which consequently controls the Pd ensemble size, illustrating the critical role of nanoscale wetting phenomena during bimetallic catalyst preparation.

36 MATERIALS SCIENCE↗

Ablation loading of barium ions into a surface-electrode trap

Trapped-ion quantum information processing may benefit from qubits encoded in isotopes that are practically available in only small quantities, e.g., due to low natural abundance or radioactivity. Laser ablation provides a method of controllably liberating neutral atoms or ions from low-volume targets, but energetic ablation products can be difficult to confine in the small ion-electrode distance, micron-scale microfabricated traps amenable to high-speed, high-fidelity manipulation of ion arrays. Here, we investigate ablation-based ion loading into surface-electrode traps of different sizes to test a model describing ion loading probability as a function of effective trap volume and other trap parameters. We characterize loading of ablated barium from a metallic source in two cryogenic surface-electrode traps with 730 and 50 μm ion-electrode distances. Furthermore, our loading rate agrees with a predictive analytical model, providing insight for the confinement of limited-quantity species of interest for quantum computing, simulation, and sensing.

74 ATOMIC AND MOLECULAR PHYSICS↗

Abundances of the elements in the solar system

The present status of abundance information for elements in meteorites and in the sun is reviewed, and a new table of abundances of the elements, which should be characteristic of the primitive solar nebula, is compiled and presented. Special attention is called to the elemental abundances in the silicon-to-calcium region, where many of the abundances are rather poorly determined, and where these abundances have an impact on theories of nucleosynthesis of the elements. To each elemental isotope is assigned a mechanism of nucleosynthesis which may have been responsible for production of most of that isotope, and brief comments are made concerning the present status of understanding of the different mechanisms of nucleosynthesis.

Cameron, A. G. W.↗

Origin of the Station 7 boulder - A note

The origin of the matrix types from the Apollo 17 Station 7 boulder is considered along with the origin of boulder material from Station 2, Boulder 1, and 73215. It is pointed out that the formation of the matrix rocks in this boulder and in the other Apollo 17 boulders in a single impact event is consistent with the isotopic evidence, ages, major-element chemistry, large ion lithophile (LIL) trace-element abundances, and textures. It had been suggested by Winzer et al. (1974), based on calculations from crystal-liquid partition coefficients for LIL trace elements, that target rocks corresponding in trace-element composition to the matrix types could have been produced by partial fusion of rocks similar to 77215. Using the same type of calculation, liquids quite similar in trace-element composition to the Station 7 boulder matrix types can be produced.

Winzer, S. R.↗

Nitrogen isotopes in lunar highlands breccias

Lunar highlands breccias from Apollo 14 and 16 which may have trapped solar wind gases at a very early epoch in the history of the moon, as implied by their high content of parentless fissiogenic xenon and sometimes of parentless radiogenic Xe-129, are analyzed for nitrogen content and isotopic composition using stepwise heating techniques. The results show that the nitrogen is not particularly light and was not acquired in very ancient times. The conflicting presence of both parentless xenon and nitrogen of relatively recent isotopic signature can be explained if the hypothetical light nitrogen is diluted by more abundant, heavier nitrogen. Accordingly, the very ancient soil components implied in these breccias by the presence of excess fission xenon were reexposed at a much later epoch, or mixed with younger soil components, before the compaction event.

Fourcade, S.↗

A Sm-Nd isotopic study of atmospheric dusts and particulates from major river systems

Nd-143/Nd-144 ratios, together with Sm and Nd abundances, are given for particulates from major and minor rivers as well as continental sediments and aeolian dusts collected over the Atlantic, Pacific, and Indian Oceans. In combination with data from the literature, the present results have implications for the age, history, and composition of the sedimentary mass and the continental crust. It is noted that the average ratio of Sm/Nd is about 0.19 in the upper continental crust, and has remained so since the early Archean, thereby precluding the likelihood of major mafic-to-felsic or felsic-to-mafic trends in the overall composition of the upper continental crust through earth history. The average 'crustal residence age' of the entire sedimentary mass is about 1.9 Ga.

Goldstein, S. L.↗

Cosmogenic helium and volatile-rich fluid in Sierra Leone alluvial diamonds

Noble gas measurements were carried out on two identical splits of a finely powdered harshly acid-washed sample derived from fragments of a single alluvial diamond from Sierra Leone, with essentially identical results obtained for both splits. Isotopic ratios for Ar, Kr, and Xe were found to be atmospheric. Their elemental abundances were high relative to published data, owing to the effect of shock implantation in the crushing step, as was verified in a supplementary experiment. No Ne was detected above the blank level. The He-3 was exceptionally abundant, while He-4 was exceptionally depleted, possibly due to the acid wash. The He-3/He-4 ratio was anomalously high at an R/Ra value of 246 + or - 16. The results support the hypothesis that the He-3 excess in diamonds is cosmogenic.

Mcconville, P.↗

The isotopic composition of cosmic-ray B, C, N, and O - Evidence for an overabundance of O-18

New observations of galactic cosmic rays at higher energies (about 400-780 MeV/nucleon) than obtained in previous direct mass measurements have resulted in determinations of the isotopic composition of B, C, N, and O. The derived cosmic-ray source abundances provide evidence for an enhancement of O-18/O-16 by a factor of 5.6 +/- 1.9 over the solar system value and give a C-13/C-12 ratio consistent with the solar system abundance ratio, but lower than some recent measurements of the local interstellar medium.

Gibner, P. S.↗

Cassini atmospheric chemistry mapper. Volume 1. Investigation and technical plan

The Cassini Atmospheric Chemistry Mapper (ACM) enables a broad range of atmospheric science investigations for Saturn and Titan by providing high spectral and spatial resolution mapping and occultation capabilities at 3 and 5 microns. ACM can directly address the major atmospheric science objectives for Saturn and for Titan, as defined by the Announcement of Opportunity, with pivotal diagnostic measurements not accessible to any other proposed Cassini instrument. ACM determines mixing ratios for atmospheric molecules from spectral line profiles for an important and extensive volume of the atmosphere of Saturn (and Jupiter). Spatial and vertical profiles of disequilibrium species abundances define Saturn's deep atmosphere, its chemistry, and its vertical transport phenomena. ACM spectral maps provide a unique means to interpret atmospheric conditions in the deep (approximately 1000 bar) atmosphere of Saturn. Deep chemistry and vertical transport is inferred from the vertical and horizontal distribution of a series of disequilibrium species. Solar occultations provide a method to bridge the altitude range in Saturn's (and Titan's) atmosphere that is not accessible to radio science, thermal infrared, and UV spectroscopy with temperature measurements to plus or minus 2K from the analysis of molecular line ratios and to attain an high sensitivity for low-abundance chemical species in the very large column densities that may be achieved during occultations for Saturn. For Titan, ACM solar occultations yield very well resolved (1/6 scale height) vertical mixing ratios column abundances for atmospheric molecular constituents. Occultations also provide for detecting abundant species very high in the upper atmosphere, while at greater depths, detecting the isotopes of C and O, constraining the production mechanisms, and/or sources for the above species. ACM measures the vertical and horizontal distribution of aerosols via their opacity at 3 microns and, particularly, at 5 microns. ACM recovers spatially-resolved atmospheric temperatures in Titan's troposphere via 3- and 5-microns spectral transitions. Together, the mixing ratio profiles and the aerosol distributions are utilized to investigate the photochemistry of the stratosphere and consequent formation processes for aerosols. Finally, ring opacities, observed during solar occultations and in reflected sunlight, provide a measurement of the particle size and distribution of ring material. ACM will be the first high spectral resolution mapping spectrometer on an outer planet mission for atmospheric studies while retaining a high resolution spatial mapping capability. ACM, thus, opens an entirely new range of orbital scientific studies of the origin, physio-chemical evolution and structure of the Saturn and Titan atmospheres. ACM provides high angular resolution spectral maps, viewing nadir and near-limb thermal radiation and reflected sunlight; sounds planetary limbs, spatially resolving vertical profiles to several atmospheric scale heights; and measures solar occultations, mapping both atmospheres and rings. ACM's high spectral and spatial resolution mapping capability is achieved with a simplified Fourier Transform spectrometer with a no-moving parts, physically compact design. ACM's simplicity guarantees an inherent stability essential for reliable performance throughout the lengthy Cassini Orbiter mission.

Smith, William Hayden↗

Evidence for a Light-Rare-Earth-Element-Depleted Source for Some Ferroan Anorthosites

In the lunar magma ocean model, ferroan anorthosites (FANs) are expected to be derived from a relatively undifferentiated source with chondritic REE abundances and yield the oldest radiometric ages of any lunar rocks. Samarium-neodymium-isotopic analyses of 60025 and 67016 yielded ages of 4.44 +/- 0.02 Ga and 4.53 +/- 0.12 Ga and initial Epsilon(sub Nd)(sup 143) values in excess of -0.5. These ages are within error of ages determined on some Mg-suite rocks by researchers. Thus, the existing data are not completely consistent with the standard magma ocean model. We have completed isotopic analysis on the pristine FAN 62236 in order to place further constraints on lunar crust-forming processes.

Borg, L. E.↗

Type I Cosmic Spherules: Key to a Major, But Poorly Sampled, Asteroid Population

Fe, Ni, and Cr abundances in Type I cosmic spherules recovered from the deep sea, and also the isotopic fractionation of these elements during passage of the spherules through the terrestrial atmosphere was determined. Isotopic fractionation for all three elements is typically large, approx. 16%o/amu, corresponding to evaporative mass losses of approx. 80-85%, assuming Rayleigh distillation from an open system. The corrected, pre-atmospheric, Cr/Ni and Fe/Ni ratios are shown, where they are compared to these ratios in bulk chondrites and chondritic metal. Although the calculated pre-atmospheric Fe/Ni ratio for the spherules is relatively constant at 19 plus or minus 4 (sigma (sub mean)), the calculated pre-atmospheric Cr/Ni ratios vary by about two orders of magnitude. The Cr/Ni ratios are thus powerful discriminators for possible modes of origin of the spherules. For example, iron meteorites typically have low Cr contents and low Cr/Ni ratios, less than or equal to 3 x 10(exp -4). Thus, Type I spherules do not appear to be ablation products of iron meteorites, in contrast to an earlier suggestion..

Nyquist, Larry E.↗

Type 1 Cosmic Spherules: Key to a Major, But Poorly Sampled, Asteroid Population?

Herzog et al. have determined Fe, Ni, and Cr abundances in Type I cosmic spherules recovered from the deep sea, and also the isotopic fractionation of these elements during passage of the spherules through the terrestrial atmosphere. Isotopic fractionation for all three elements is typically large, approx.16%(sigma)/amu, corresponding to evaporative mass losses of approx.80-85%, assuming Rayleigh distillation from an open system. The corrected, pre-atmospheric, Cr/Ni and Fe/Ni ratios are shown in Figure 1, where they are compared to these ratios in bulk chondrites and chondritic metal. Although the calculated pre-atmospheric Fe/Ni ratio for the spherules is relatively constant at 19+/-4 (sigma(sub mean), the calculated pre-atmospheric Cr/Ni ratios vary by about two orders of magnitude. The Cr/Ni ratios are thus powerful discriminators for possible modes of origin of the spherules. For example, iron meteorites typically have low Cr contents and low Cr/Ni ratios,:less than or equal to 3 x 10(exp -4). Thus, Type I spherules do not appear to be ablation products of iron meteorites, in contrast to an earlier suggestion.

Nyquist, L. E.↗

Type I Cosmic Spherules: Key to a Major, But Poorly Sampled, Asteroid Population?

Herzog et al. have determined Fe, Ni, and Cr abundances in Type I cosmic spherules recovered from the deep sea, and also the isotopic fractionation of these elements during passage of the spherules through the terrestrial atmosphere. Isotopic fractionation for all three elements is typically large, approx. 16%/amu, corresponding to evaporative mass losses of approx. 80 - 85%, assuming Rayleigh distillation from an open system. The corrected, pre-atmospheric, Cr/Ni and Fe/Ni ratios, are compared to ratios in bulk chondrites and chondritic metal. Although the calculated pre-atmospheric Fe/Ni ratio for the spherules is relatively constant at 19 +/- 4 (sigma(sub mean)) the calculated pre-atmospheric Cr/Ni ratios vary by about two orders of magnitude. The Cr/Ni ratios are thus powerful discriminators for possible modes of origin of the spherules. For example, iron meteorites typically have low Cr contents and low Cr/Ni ratios, less or = 3 x 10(exp -4). Thus, Type I spherules do not appear to be ablation products of iron meteorites, in contrast to an earlier suggestion.

Nyquist, L. E.↗

Carbonate petrography, kerogen distribution, and carbon and oxygen isotope variations in an early Proterozoic transition from limestone to iron-formation deposition, Transvaal Supergroup, South Africa

The transition zone comprises Campbellrand microbialaminated (replacing "cryptalgalaminate") limestone and shale, with minor dolomite, conformably overlain by the Kuruman Iron Formation of which the basal part is characterized by siderite-rich microbanded iron-formation with minor magnetite and some hematite-containing units. The iron-formation contains subordinate intraclastic and microbialaminated siderite mesobands and was deposited in deeper water than the limestones. The sequence is virtually unaltered with diagenetic mineral assemblages reflecting a temperature interval of about 110 degrees to 170 degrees C and pressures of 2 kbars. Carbonate minerals in the different rock types are represented by primary micritic precipitates (now recrystallized to microsparite), early precompactional sparry cements and concretions, deep burial limpid euhedral sparites, and spar cements precipitated from metamorphic fluids in close contact with diabase sills. Paragenetic pathways of the carbonate minerals are broadly similar in all lithofacies with kerogen intimately associated with them. Kerogen occurs as pigmentation in carbonate crystals, as reworked organic detritus in clastic-textured carbonate units, and as segregations of kerogen pigment around late diagenetic carbonate crystals. Locally kerogen may also be replaced by carbonate spar. Carbon isotope compositions of the carbonate minerals and kerogen are dependent on their mode of occurrence and on the composition of the dominant carbonate species in a specific lithofacies. Integration of sedimentary, petrographic, geochemical, and isotopic results makes it possible to distinguish between depositional, early diagenetic, deep burial, and metamorphic effects on the isotopic compositions of the carbonate minerals and the kerogen in the sequence. Major conclusions are that deep burial thermal decarboxylation led to 13C depletion in euhedral ferroan sparites and 13C enrichment in kerogen (organic carbon). Metamorphic sparites are most depleted in 13C. Carbonates in oxide-rich iron-formations are more depleted in 13C than those in siderite-rich iron-formation whereas the kerogens in oxide banded iron-formations (BIF) are more enriched. This implies that the siderite-rich iron-formations were not derived from oxide-rich iron-formation through reduction of ferric iron by organic matter. Organic matter oxidation by ferric iron did, however, decrease the abundance of kerogen in oxide-rich iron-formation and led to the formation of isotopically very light sparry carbonates. Siderite and calcmicrosparite both represent recrystallized primary micritic precipitates but differ in their 13C composition, with the siderites depleted in 13C by 4.6 per mil on average relative to calcmicrosparite. This means that the siderites were precipitated from water with dissolved inorganic carbon depleted in 13C by about 9 per mil relative to that from which the limestones precipitated. This implies an ocean system stratified with regard to total carbonate, with the deeper water, from which siderite-rich iron-formation formed, depleted in 13C. Iron-formations were deposited in areas of very low organic matter supply. Depletion of 13C may, therefore, derive not from degradation of organic matter but from hydrothermal activity, a conclusion which is supported by 18O composition of the carbonate minerals and trace element and rare earth element (REE) compositions of the iron-formations.

NASA Discipline Number 52-30↗