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The topics discussed include the following: noble gas content and release temperatures; trace element abundances; heating summary of cluster fragments; isotopic measurements; and trace organic chemistry.
Elemental and isotopic abundances of Ar and Xe were measured in three grain-size separates in the dark phase of the enstatite achondrite Pesyanoe by stepwise heating, using a combination of pyrolysis and combustion steps. The data reveal a low-temperature gas fraction with Ar/Xe ratios close to the solar ratio and isotopically similar to solar-type Ar and Xe observed in lunar samples. The gas released at intermediate temperature steps shows that Ar and Xe are isotopically fractionated, compared to the low-temperature components. Pesyanoe does not have excess Ar-40 and fission Xe, which means its parent body was too small for ion reimplantation. It is concluded that solar-type Xe isotopic abundances can be inferred from the low-temperature component. A comparison of Pesyanoe and lunar data shows that isotopic signatures of solar-wind Xe, as sampled at two different points in solar system space and time, are identical within experimental error.
Subtle variations in stable isotope ratios at natural abundance are challenging to measure but can yield critical insights into biological, physical, and geochemical processes. Well established methods, particularly multi-collector, gas-source or plasma isotope ratio mass spectrometry (IRMS) are the gold standard for stable isotope measurement but inherent limitations in these approaches make them ill-suited to determining site-specific and multiply substituted isotopic abundances of all but a few compounds, or to characterizing mixtures or larger intact molecules. Additionally, Fourier transform mass spectrometry (FTMS), namely Orbitrap mass spectrometry, has recently demonstrated the ability to measure natural abundance isotope ratios with chemically informative accuracy and precision. Here, we report the first use of Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) for the accurate (<1‰) and precise (<1‰ standard error) simultaneous determination of $δ$ 13 C and $δ$ 15 N in caffeine isotopologues and provide a discussion of the critical instrumental parameters necessary to make such measurements. Finally, we report the ability to make these measurements with online liquid chromatography, expanding the ability of this technique to explore mixtures in the future.
The fractional abundances of the isotopic species of carbon monoxide in interstellar clouds are calculated on a basis of gas-phase ion-molecule reactions. The (C-13)O/(C-12)O ratio varies significantly with extinction of the ultraviolet radiation field, and in the outer regions of dark dense clouds (C-13)O may be enhanced by a factor of 10. The observational interpretation of the CO to H2 or interstellar-reddening relation and the isotopic abundances of carbon are complicated by these effects.
An instrument, the Caltech High Energy Isotope Spectrometer Telescope was developed to measure isotopic abundances of cosmic ray nuclei by employing an energy loss - residual energy technique. A detailed analysis was made of the mass resolution capabilities of this instrument. A formalism, based on the leaky box model of cosmic ray propagation, was developed for obtaining isotopic abundance ratios at the cosmic ray sources from abundances measured in local interstellar space for elements having three or more stable isotopes, one of which is believed to be absent at the cosmic ray sources. It was shown that the dominant sources of uncertainty in the derived source ratios are uncorrelated errors in the fragmentation cross sections and statistical uncertainties in measuring local interstellar abundances. These results were applied to estimate the extent to which uncertainties must be reduced in order to distinguish between cosmic ray production in a solar-like environment and in various environments with greater neutron enrichments.
Apollo 11 lunar material actinide element abundance and isotopic composition, examining Th, U and transuranium elements by mass spectrometric and radiometric techniques
The design and demonstration of an optical analysis system based on wavelength modulation spectroscopy in an atomic beam for uranium isotope abundance determinations is presented. This system probes the uranium 5f 3 6d7s 2 ( 5 L 6 ) → 5f 2 6d 2 7s 2 ( 5 K 5 ) transition at 861.031 nm, which is considered to be the most suitable transition for uranium isotopic analysis. A new laser characterization strategy was developed for the conditions where optimum laser wavelength modulation depth was small compared to the free spectral range (FSR) of etalons. Two capabilities enabled the higher-precision determination of isotope abundances of atomic beams: (1) reduction of low-frequency additive noise, especially the noise caused by black-body radiation and (2) suppression of non-absorption transmission losses. The performance of this system was validated with uranium samples of various isotopic compositions. Further, by comparing the measurements using natural uranium samples between the direct absorption and the wavelength modulation approaches, a 21-fold decrease in uncertainty of the integrated absorbance and a 6.8-fold improvement in the 1-σ precision of the number density were achieved. In addition, by comparing the results using uranium oxide samples, a 6.1-fold decrease in the uncertainty of inferred isotope abundance was obtained. These results demonstrate that the 1f-normalized 2f wavelength modulation spectroscopy (WMS-2f/1f) technique enables higher-precision analysis of atomic beams.
Measurements of the isotopic composition of cosmic rays have shown that the cosmic ray isotope ratios, Ne-22/Ne-20 and (Mg-25 + Mg-26)/Mg-24, exceed the solar abundance ratios by factors of 2.7 and 1.8, respectively. There are several processes which could be responsible for the observed excess of neutron-rich isotopes. The considered models imply neutron enrichment in the case of other, less abundant species, and a measurement of the involved isotopic abundances could provide a basis for the determination of the dominating processes occurring in cosmic ray sources. However, an experiment utilizing special equipment is necessary to conduct the required measurements. Such an experiment, the Aluminum Isotopic Composition Experiment (Alice), is being designed in a joint effort involving NASA and a West German university. Alice uses a Cherenkov-range technique to determine the isotopic composition of elements from oxygen through argon.
Isotopic abundance and content of sulfur in stony and iron meteorites
Isotopic abundance and content used to trace history of 20 iron and stony meteorites
The cosmic ray source charge and isotopic abundances for charges with Z = 9-16 are reexamined using newly measured fragmentation cross sections in a standard Galactic propagation model. Compared with earlier studies, the cosmic-ray data are now consistent with no excess of Si-29 and Si-30 in the source relative to the solar coronal abundances. The excess of Mg-25 and Mg-26 is now about 1 sigma or less relative to solar coronal isotopic abundances, leaving Ne-22 as the only clearly established neutron-rich isotopic excess in the cosmic ray source. Better estimates of the source abundances of elements obtained using the new cross sections permit the conclusion that high first ionization potential (FIP) elements have a wide spread of compositional differences in the cosmic-ray source relative to solar coronal abundances, whereas elements with a low FIP have a composition similar to the solar corona.
Resonance ionization mass spectrometry (RIMS) is a relatively new laser-based technique for the determination of isotopic abundances. The resonance ionization process depends upon the stepwise absorption of photons from the laser, promoting atoms of the element of interest through progressively higher electronic states until an ion is formed. Sensitivity arises from the efficiency of the resonant absorption process when coupled with the power available from commercial laser sources. Selectivity derives naturally from the distinct electronic structure of different elements. This isobaric discrimination has provided the major impetus for development of the technique. Resonance ionization mass spectrometry was used for analysis of the isotopic abundances of the rare earth lutetium. Isobaric interferences from ytterbium severely effect the ability to measure small amounts of the neutron-deficient Lu isotopes by conventional mass spectrometric techniques. Resonance ionization for lutetium is performed using a continuous-wave laser operating at 452 nm, through a sequential two-photon process, with one photon exciting the intermediate resonance and the second photon causing ionization. Ion yields for microgram-sized quantities of lutetium lie between 10(6) and 10(7) ions per second, at overall ionization efficiencies approaching 10(-4). Discrimination factors against ytterbium greater than 10(6) have been measured. Resonance ionization for technetium is also being explored, again in response to an isobaric interference, molybdenum. Because of the relatively high ionization potential for Tc, three-photon, two-color RIMS processes are being developed.
The Viking gas chromatograph mass spectrometer experiment provided significant data on the atmospheric composition at the surface of Mars, including measurements of several isotope ratios. However, the limited dynamic range of this mass spectrometer resulted in marginal measurements for the important Kr and Xe isotopic abundance. The Xe-129 to Xe-132 ratio was measured with an uncertainty of 70%, but none of the other isotope ratios for these species were obtained. Accurate measurement of the Xe and Kr isotopic abundance in this atmosphere provides an important data point in testing theories of planetary formation and atmospheric evolution. The measurement is also essential for a stringent test for the Martian origin of the SNC meteorites, since the Kr and Xe fractionation pattern seen in gas trapped in glassy nodules of an SNC (EETA 79001) is unlike any other known solar system resevoir. Current flight mass spectrometer designs combined with the new technology of a high-performance vacuum pumping system show promise for a substantial increase in gas throughput and the dynamic range required to accurately measure these trace species. Various aspects of this new technology are discussed.
Isotopic abundances and composition of U and Th in Apollo 12 soil and breccia samples, using mass spectroscopy
Results of microwave measurements in dense interstellar clouds are discussed which pertain to determinations of relative isotopic abundances. Difficulties in deriving relative abundances from observations of the relative intensities of isotopic lines are examined, and measures available for coping with these complications are outlined. Results are presented concerning the relative abundances of C-13, O-17, O-18, N-15, Si-30, S-33, S-34, and D in a variety of interstellar clouds; the consistency of these results is evaluated. It is concluded that: (1) the relative abundances of C-13 and O-17 in interstellar clouds are generally higher than those in the solar system; (2) the abundances of N-15 and D are lower than the solar-system values; (3) the O-18 abundance is possibly higher than in the solar system; and (4) there are substantial variations in the isotopic abundances between different large interstellar clouds, with some of these variations not dependent on distance from the galactic center alone.
Coronal isotopic abundances for the elements He, C, N, O, Ne, and Mg are derived from previously published measurements of the isotopic composition of solar energetic particles by first measuring, and then correcting for, the charge-to-mass-dependent fractionation due to solar flare acceleration and propagation processes. The resulting coronal composition generally agrees with that of other samples of solar system material, but the previously noted difference between the solar flare and solar wind Ne-22/Ne-20 ratios remains unresolved.
Relative isotopic abundance of potassium 40 in terrestrial and meteoritic samples
A formalism has been developed for deriving cosmic-ray source isotopic abundances from observed local abundances using a purely secondary nuclide as a tracer of spallation production during propagation. Although the formalism is based on the leaky-box model of cosmic-ray propagation, it is shown that source abundances derived by the tracer technique are reasonably independent of detailed propagation models. The tracer formalism also permits a quantitative evaluation of the effects of observational uncertainties on deduced source abundances. It is shown that statistical errors in the observed abundances and uncertainties in the spallation cross sections are at present the dominant sources of uncertainty. The latter error can be reduced with increased detector size or exposure time, while the former can be minimized by measurements of the relative production cross sections. As a specific example, the tracer technique is applied to the isotopes of sulfur and calcium, and the level of uncertainties which must be achieved to distinguish evolutionary differences between solar-system material and cosmic ray-source material are established.