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At least 19 records

Isotope shifts in methane near 6000/cm

Isotope shifts for cleanly resolved vibrational-rotational absorption lines of CH4-12 and CH4-13 were measured by a 5-m focal length Littrow spectrometer in the 6000/cm range. The methane isotopes were held in separate absorption cells: 20 torr of CH4-13 in a 1-m cell, and 5 torr of CH4-12 in a White cell of 4-m optical path length. Measured shifts for the cleanly resolved singlets R(0), R(1), Q(1) and P(1) are summarized in tabular form.

Fox, K.↗

First Principle Predictions of Isotopic Shifts in H2O

We compute isotope independent first and second order corrections to the Born-Oppenheimer approximation for water and use them to predict isotopic shifts. For the diagonal correction, we use icMRCI wavefunctions and derivatives with respect to mass dependent, internal coordinates to generate the mass independent correction functions. For the non-adiabatic correction, we use scaled SCF/CIS wave functions and a generalization of the Handy method to obtain mass independent correction functions. We find that including the non-adiabatic correction gives significantly improved results compared to just including the diagonal correction when the Born-Oppenheimer potential energy surface is optimized for H2O-16. The agreement with experimental results for deuterium and tritium containing isotopes is nearly as good as our best empirical correction, however, the present correction is expected to be more reliable for higher, uncharacterized levels.

Schwenke, David W.↗

Possible isotopic shifts with changes in the geomagnetic field

The geomagnetic fields of the past geological epochs are studied on the basis of observations on the rock residual magnetization. This paper evaluates the shifts in the isotopic composition of the same elements in the rocks affected by cosmic rays. The possibility of using the shifts in the isotopic composition for revealing geomagnetic field inversions is discussed. Geomagnetic field inversion periods traced by the rock residual magnetization are in good agreement with the periods of the greatest qualitative changes in the animal world throughout the last 500 million years.

Bulashevich, Y. P.↗

Hyperfine structure and isotope shifts of transitions in neutral and singly ionized ytterbium

The present experimental investigation of the hyperfine structure and isotopic shifts of transitions in neutral and singly-ionized Yb, which constitute a system of some interest to microwave-frequency standards, used counterpropagating pump and probe laser beams directed through a hollow-cathode discharge lamp. The results obtained are in agreement with previous measurements except in the case of the Yb-173(+) 6 2P0 sub 3/2 state, which is more accurately determined.

Berends, R. W.↗

Precise laser frequency scanning using frequency-synthesized optical frequency sidebands - Application to isotope shifts and hyperfine structure of mercury

Based on an efficient broadband electrooptic modulator producing RF optical sidebands locked to a stable cavity, a tunable dye laser can be scanned under computer control with frequency-synthesizer precision. Cavity drift is suppressed in software by using a strong feature in the spectrum for stabilization. Mercury isotope shifts are measured with a reproducibility of about 50 kHz. This accuracy of about 1/300 of the linewidth illustrates the power of the technique. Derived hyperfine-structure constants are compared with previous atomic-beam data.

Rayman, M. D.↗

Rare earth element transport in the western North Atlantic inferred from Nd isotopic observations

The relationship between the Nd isotopic composition in the Atlantic waters and the origin and circulation of the water masses was investigated. Samples were collected in the western North Atlantic between 7 and 54 deg N. The isotopic composition (Nd-143/Nd-144 ratios) showed extensive vertical structure at all locations. In regions where a thermocline was well-developed, large isotopic shifts were observed across the base of the thermocline, while regions without a thermocline were characterized by much more gradual shifts in isotopic composition with depth. The data reveal an excellent correlation between the Nd isotopic distribution in the western North Atlantic water column and the distribution of water masses identified from temperature and salinity measurements.

Piepgras, D. J.↗

Lower limit to the interstellar C 12/C 13 ratio in the direction of 20 Tauri.

Results of photoelectric scanning of the spectrum of 20 Tau in the vicinity of 4232 A of interstellar CH(+). From the observed absence of the isotopically shifted line of super 13CH(+) it is deduced that the C 12/C 13 isotopic abundance ratio in this direction is greater than 33, and hence consistent with the terrestrial value.

Vanden Bout, P.↗

Abrupt Changes at the Permian/Triassic Boundary: Tempo of Events from High-Resolution Cyclostratigraphy

The Permian/Triassic (P/Tr) boundary (251.4 +/- 3 Myr) is marked by the most severe mass extinction in the geologic record. Recently, precise absolute dating has bracketed the marine extinctions and associated carbon-isotope anomaly within less than 1 Myr. We improve this resolution through high-resolution stratigraphy across the P/Tr boundary in the 331-m Gartnerkofel-1 core and nearby Reppwand outcrop section (Carnic Alps, Austria) utilizing FFT and wavelet timeseries analyses of cyclic components in down-hole core logs of density and natural gamma-ray intensity, and carbon-isotopic ratios of bulk samples. The wavelet analysis indicates continuity of deposition across the P/Tr boundary interval, and the timeseries analyses show evidence for persistent cycles in the ratio of approximately 40: 10: 4.7: 2.3 meters, correlated with Milankovitch-band orbital cycles of approximately 412: 100: 40: 20 kyr (eccentricity 1 and 2, obliquity, and precession), and giving a consistent average sedimentation rate of approximately 10 cm/1,000 yr. Milankovitch periods in delta C-13 and density in these shallow-water carbonates were most likely the result of climatically induced oscillations of sea level and climate, coupled with changes in ocean circulation and productivity, that affected sedimentation. Fluctuations in gamma radiation reflect varying input of clay minerals and the presence of shaly interbeds. Throughout the P/Tr boundary interval in the core, the 100,000-year eccentricity cycle seems to be dominant. Weaker obliquity and precession cycles are in line with the location of the Austrian section in the latest Permian, close to the Equator in the western bight of the Tethys, where obliquity and precessional effects on seasonal contrast might be subdued. Using the improved resolution provided by cycle analysis in the GK-1 core, we find that the dramatic change in the faunal record that marks the P/Tr boundary takes place over less than 6m, or less than 60,000 years. In the nearby Reppwand outcrop section, the same faunal changes occurs over only 0.8 m or about 8,000 years, close to the limit of time-resolution induced by bioturbation and reworking in these sediments. The sharp negative global carbon-isotope shift took place within less than or equal to 40,000 yr, and the isotope excursions persisted for approximately 480,000 yr into the Early Triassic. The results indicate that the severe marine faunal event that marks the P/Tr boundary was very sudden, perhaps less than the resolution window in the GK-1 core, and suggest a catastrophic cause. The wavelet-analysis approach to high-resolution cyclostratigraphy can be applied to other P/Tr boundary sections, and when combined with precise absolute dating and magnetostratigraphic methods promises a significant increase in resolution in determining the correlation and tempo of the end-Permian extinctions and related events worldwide.

Rampino, M. R.↗

Coordinated Isotopic and Mineral Characterization of Highly Fractionated 18O-Rich Silicates in the Queen Alexandra Range 99177 CR3 Chondrite

Carbonaceous chondrites contain a mixture of solar system condensates, pre-solar grains, and primitive organic matter. Each of these materials record conditions and processes in different regions of the solar nebula, on the meteorite parent body, and beyond the solar system. Oxygen isotopic studies of meteorite components can trace interactions of distinct oxygen isotopic reservoirs in the early solar system and secondary alteration processes. The O isotopic compositions of the earliest solar system condensates fall along a carbonaceous chondrite anhydrous mineral (CCAM) line of slope approximately 1 in a plot of delta 17O against delta 18O. This trend is attributed to mixing of material from 16O-poor and 16O-rich reservoirs. Secondary processing can induce mass-dependent fractionation of the O isotopes, shifting these compositions along a line of slope approximately 0.52. Substantial mass-dependent fractionation of O isotopes has been observed in secondary minerals in CAIs, calcite, and FUN inclusions. These fractionations were caused by significant thermal or aqueous alteration. We recently reported the identification of four silicate grains with extremely fractionated O isotopic ratios (delta 18O equals 37 - 55 per mille) in the minimally altered CR3 chondrite QUE 99177. TEM analysis of one grain indicates it is a nebular condensate that did not experience substantial alteration. The history of these grains is thus distinct from those of the aforementioned fractionated materials. To constrain the origin of the silicate grains, we conducted further Mg and Fe isotopic studies and TEM analyses of two grains.

Nguyen, A. N.↗

Sedimentary organic molecules: Origins and information content

To progress in the study of organic geochemistry, we must dissect the processes controlling the composition of sedimentary organic matter. Structurally, this has proven difficult. Individual biomarkers can often be recognized, but their contribution to total organic materials is small, and their presence does not imply that their biochemical cell mates have survived. We are finding, however, that a combination of structural and isotopic lines of evidence provides new information. A starting point is provided by the isotopic compositions of primary products (degradation products of chlorophylls, alkenones derived from coccoliths). We find strong evidence that the isotopic difference between primary carbonate and algal organic material can be interpreted in terms of the concentration of dissolved CO2. Moreover, the isotopic difference between primary and total organic carbon can be interpreted in terms of characteristic isotopic shifts imposed by secondary processes (responsive, for example, to O2 levels in the depositional environment. In favorable cases, isotopic compositions of a variety of secondary products can be interpreted in terms of flows of carbon, and, therefore, in terms of specific processes and environmental conditions within the depositional environment.

Hayes, J. M.↗

Mantle rare gas relative abundances in a steady-state mass transport model

A model for He and Xe was presented previously which incorporates mass transfer of rare gases from an undegassed lower mantle (P) and the atmosphere into a degassed upper mantle (D). We extend the model to include Ne and Ar. Model constraints on rare gas relative abundances within P are derived. Discussions of terrestrial volatile acquisition have focused on the rare gas abundance pattern of the atmosphere relative to meteoritic components, and the pattern of rare gases still trapped in the Ear,th is important in identifying volatile capture and loss processes operating during Earth formation. The assumptions and principles of the model are discussed in Wasserburg and Porcelli (this volume). For P, the concentrations in P of the decay/nuclear products 4 He, 21 Ne, 40 Ar, and 136 Xe can be calculated from the concentrations of the parent elements U, Th, K, and Pu. The total concentration of the daughter element in P is proportional to the isotopic shifts in P. For Ar, ((40)Ar/(36)Ar)p - ((40)Ar/(36)Ar)o =Delta (exp 40) p= 40 Cp/(exp 36)C where(i)C(sub j) the concentration of isotope i in j. In D, isotope compositions are the result of mixing rare gases from P, decay/nuclear products generated in the upper mantle, and subducted rare gases (for Ar and Xe).

Porcelli, D.↗