Evidence for O-atom exchange in the O(^1D) + N_2O reaction as the source of mass-independent isotopic fractionation in atmospheric N_2O

Recent experiments have shown that in the oxygen isotopic exchange reaction for O(^1D) + CO_2 the elastic channel is approximately 50% that of the inelastic channel [Perri et al., 2003]. We propose an analogous oxygen atom exchange reaction for the isoelectronic O(^1D) + N_2O system to explain the mass-independent isotopic fractionation (MIF) in atmospheric N_2O. We apply quantum chemical methods to compute the energetics of the potential energy surfaces on which the O(^1D) + N_2O reaction occurs. Preliminary modeling results indicate that oxygen isotopic exchange via O(^1D) + N_2O can account for the MIF oxygen anomaly if the oxygen atom isotopic exchange rate is 30–50% that of the total rate for the reactive channels

An isotopic effect in phi photoproduction at a few GeV

A distinct isotopic effect in phi photoproduction at 2-5 GeV region is identified by examining the production amplitudes due to Pomeron-exchange and meson-exchange mechanisms. This effect is mainly caused by the pi-eta interference constrained by SU(3) symmetry and the isotopic structure of the gamma NN coupling in the direct phi-radiation amplitude. It can be tested experimentally by measuring differences in the polarization observables between the gamma-p and gamma-n reactions.Comment: 11 pages, 6 figure

Hubble Space Telescope Survey of Interstellar ^12CO/^13CO in the Solar Neighborhood

We examine 20 diffuse and translucent Galactic sight lines and extract the column densities of the ^12CO and ^13CO isotopologues from their ultraviolet A--X absorption bands detected in archival Space Telescope Imaging Spectrograph data with lambda/Deltalambda geq 46,000. Five more targets with Goddard High-Resolution Spectrograph data are added to the sample that more than doubles the number of sight lines with published Hubble Space Telescope observations of ^13CO. Most sight lines have 12-to-13 isotopic ratios that are not significantly different from the local value of 70 for ^12C/^13C, which is based on mm-wave observations of rotational lines in emission from CO and H_2CO inside dense molecular clouds, as well as on results from optical measurements of CH^+. Five of the 25 sight lines are found to be fractionated toward lower 12-to-13 values, while three sight lines in the sample are fractionated toward higher ratios, signaling the predominance of either isotopic charge exchange or selective photodissociation, respectively. There are no obvious trends of the ^12CO-to-^13CO ratio with physical conditions such as gas temperature or density, yet ^12CO/^13CO does vary in a complicated manner with the column density of either CO isotopologue, owing to varying levels of competition between isotopic charge exchange and selective photodissociation in the fractionation of CO. Finally, rotational temperatures of H_2 show that all sight lines with detected amounts of ^13CO pass through gas that is on average colder by 20 K than the gas without ^13CO. This colder gas is also sampled by CN and C_2 molecules, the latter indicating gas kinetic temperatures of only 28 K, enough to facilitate an efficient charge exchange reaction that lowers the value of ^12CO/^13CO.Comment: 1-column emulateapj, 23 pages, 9 figure

A theoretical study of ozone isotopic effects using a modified ab initio potential energy surface

A modified ab initio potential energy surface (PES) is used for calculations of ozone recombination and isotopic exchange rate constants. The calculated low-pressure isotopic effects on the ozone formation reaction are consistent with the experimental results and with the theoretical results obtained earlier [J. Chem. Phys. 116, 137 (2002)]. They are thereby relatively insensitive to the properties of these PES. The topics discussed include the dependence of the calculated low-pressure recombination rate constant on the hindered-rotor PES, the role of the asymmetry of the potential for a general X + YZ reaction (Y[not-equal]Z), and the partitioning to form each of the two recombination products: XYZ and XZY

Stable isotopic disequilibrium in high-T metamorphic systems

A principal use of stable isotopes in metamorphic rocks is as thermometers, or as tests for isotopic equilibrium where metamorphic temperatures are known. Applications are often complicated when apparent isotopic temperatures are discordant and disagree with petrologic temperatures, indicating a failure of isotopic systems to record and/or preserve equilibrium, peak-T fractionations. In low-T, fluid-hosted environments such features often clearly reflect open system exchange. However, in high-T metamorphic environments a slow cooling history can be sufficient to produce such features by retrograde, closed system exchange between coexisting minerals

Predicted Diurnal Variation of the Deuterium to Hydrogen Ratio in Water at the Surface of Mars Caused by Mass Exchange with the Regolith

Regolith on Mars exchanges water with the atmosphere on a diurnal basis and this process causes significant variation in the abundance of water vapor at the surface. While previous studies of regolith-atmosphere exchange focus on the abundance, recent in-situ experiments and remote sensing observations measure the isotopic composition of the atmospheric water. We are therefore motivated to investigate isotopic water exchange between the atmosphere and the regolith and determine its effect on the deuterium to hydrogen ratio (D/H) of the atmosphere. We model transport of water in the regolith and regolith-atmosphere exchange by solving a transport equation including regolith adsorption, condensation, and diffusion. The model calculates equilibrium fractionation between HDO and H2O in each of these processes. The fractionation in adsorption is caused by the difference in the latent heat of adsorption, and that of condensation is caused by the difference in the vapor pressure. Together with a simple, bulk-aerodynamic boundary layer model, we simulate the diurnal variation of the D/H near the planetary surface. We find that the D/H can vary by 300 - 1400 per mil diurnally in the equatorial and mid-latitude locations, and the magnitude is greater at a colder location or season. The variability is mainly driven by adsorption and desorption of regolith particles, and its diurnal trend features a drop in the early morning, a rise to the peak value during the daytime, and a second drop in the late afternoon and evening, tracing the water vapor flow into and out from the regolith. The predicted D/H variation can be tested with in-situ measurements. As such, our calculations suggest stable isotope analysis to be a powerful tool in pinpointing regolith-atmosphere exchange of water on Mars.Comment: Accepted by Earth and Planetary Science Letter

Global modelling of H2 mixing ratios and isotopic compositions with the TM5 model

The isotopic composition of molecular hydrogen (H2) contains independent information for constraining the global H2 budget. To explore this, we have implemented hydrogen sources and sinks, including their isotopic composition, into the global chemistry transport model TM5. For the first time, a global model now includes a simplified but explicit isotope reaction scheme for the photochemical production of H2. We present a comparison of modelled results for the H2 mixing ratio and isotope composition with available measurements on the seasonal to inter annual time scales for the years 2001–2007. The base model results agree well with observations for H2 mixing ratios. For dD[H2], modelled values are slightly lower than measurements. A detailed sensitivity study is performed to identify the most important parameters for modelling the isotopic composition of H2. The results show that on the global scale, the discrepancy between model and measurements can be closed by adjusting the default values of the isotope effects in deposition, photochemistry and the stratosphere-troposphere exchange within the known range of uncertainty. However, the available isotope data do not provide sufficient information to uniquely constrain the global isotope budget. Therefore, additional studies focussing on the isotopic composition near the tropopause and on the isotope effects in the photochemistry and deposition are recommended

The effect of pH of water on the measurement of oxygen isotopic ratio by means of CO(2)-H(2)O isotopic exchange technique

The effect of pH of water on the measurement of oxygen isotopic ratio by means of CO(2)-H(2)O isotopic exchange technique was studied. In this study, a new type of reaction vessel was used (Fig. 1). The reaction time for equilibration using this new reaction vessel was nearly equal to that in the previous study (Fig. 2). The oxygen isotopic ratios of each two samples of pH 2, 4, 7, 8, 9, and 10 were measured. There is no significant difference between the observed δ(18)O values of these samples (Table 1). Therefore it is concluded that the effect of pH of water needs not to be taken into account on the measurement of oxygen isotopic ratio by means of CO(2)-H(2)O isotopic exchange technique