Isotopic exchange between carbon dioxide and ozone via O(1D) in the stratosphere.

We propose a novel mechanism for isotopic exchange between CO2 and O3 via O(1D) + CO2 --> CO3* followed by CO3* --> CO2 + O(3P). A one-dimensional model calculation shows that this mechanism can account for the enrichment in 18O in the stratospheric CO2 observed by Gamo et al. [1989], using the heavy O3 profile observed by Mauersberger [1981]. The implications of this mechanism for other stratospheric species and as a source of isotopically heavy CO2 in the troposphere are briefly discussed.

[1]  J. Kaye.  Analysis of the origins and implications of the18O content of stratospheric water vapor , 1990 .

[2]  M. Allen,et al.  El Chichon volcanic aerosols: impact of radiative, thermal, and chemical perturbations. , 1989, Journal of geophysical research.

[3]  I. Nolt,et al.  Stratospheric H218O distribution from far infrared observations , 1989 .

[4]  Frank J. Murcray,et al.  Isotopic abundances of stratopheric ozone from balloon‐borne high‐resolution infrared solar spectra , 1989 .

[5]  T. Nakazawa,et al.  Carbon and oxygen isotopic ratios of carbon dioxide of a stratospheric profile over Japan , 1989 .

[6]  K. Mauersberger,et al.  Laboratory measurements of ozone isotopomers by tunable diode laser absorption spectroscopy , 1989 .

[7]  C. J. Howard,et al.  Oxygen atom exchange in the interaction of hydroxyl-(18OH) with several small molecules , 1989 .

[8]  K. Mauersberger,et al.  Oxygen fractionation of ozone isotopes 48O3 through 54O3 , 1989 .

[9]  M. Thiemens,et al.  New experimental evidence for the mechanism for production of isotopically heavy O3 , 1988 .

[10]  Mian M. Abbas,et al.  Heavy ozone distribution in the stratosphere from far-infrared observations , 1987 .

[11]  Jack A. Kaye,et al.  Mechanisms and observations for isotope fractionation of molecular species in planetary atmospheres , 1987 .

[12]  S. Epstein,et al.  The effect of pressure and excitation energy on the isotopic fractionation in the formation of ozone by discharge of O2 , 1987 .

[13]  S. Epstein,et al.  The effect of the isotopic composition of oxygen on the non-mass-dependent isotopic fractionation in the formation of ozone by discharge of O2. [from meteorites] , 1987 .

[14]  J. Valentini.  Mass‐independent isotopic fractionation in nonadiabatic molecular collisions , 1987 .

[15]  P. Tans,et al.  Latitudinal variation in oxygen-18 of atmospheric CO2 , 1987, Nature.

[16]  H. Friedli,et al.  Measurements of concentration, 13C/12C and 18O/16O ratios of tropospheric carbon dioxide over Switzerland , 1987 .

[17]  H. Oeschger,et al.  Measurements of concentration, 13 C/ 12 C and 18 O/ 16 O ratios of tropospheric carbon dioxide over Switzerland , 1987 .

[18]  Konrad Mauersberger,et al.  Ozone isotope measurements in the stratosphere , 1987 .

[19]  D. R. Bates.  Heavy ozone in the stratosphere , 1986 .

[20]  Jack A. Kaye,et al.  Theoretical analysis of isotope effects on ozone formation in oxygen photochemistry , 1986 .

[21]  M. Thiemens,et al.  A non‐mass‐dependent oxygen isotope effect in the production of ozone from molecular oxygen: The role of molecular symmetry in isotope chemistry , 1986 .

[22]  L. Froidevaux,et al.  A critical analysis of CL0 and 03 in the mid-latitude stratosphere , 1985 .

[23]  V. Malathy Devi,et al.  Identification of 18O-isotopic lines of ozone in infrared ground-based solar absorption spectra , 1985 .

[24]  M. Molina,et al.  Chemical kinetics and photochemical data for use in stratospheric modeling , 1985 .

[25]  S. Gibson,et al.  Photodissociation of 16O18O in the atmosphere , 1984 .

[26]  Charles D. Keeling,et al.  Seasonal, latitudinal, and secular variations in the abundance and isotopic ratios of atmospheric CO2: 2. Results from oceanographic cruises in the tropical Pacific Ocean , 1984 .

[27]  R. D. Zafra,et al.  A measurement of stratospheric HO2 by ground‐based millimeter‐wave spectroscopy , 1984 .

[28]  D. Strobel,et al.  Enhancement of heavy ozone in the Earth's atmosphere? , 1983 .

[29]  B. Carli,et al.  New assignments in the submillimeter emission spectrum of the stratosphere , 1982 .

[30]  K. Mauersberger.  Mass spectrometry in the stratosphere , 1982 .

[31]  Konrad Mauersberger,et al.  Measurement of heavy ozone in the stratosphere , 1981 .

[32]  K. Mauersberger,et al.  Calibration of a mass spectrometer experiment for ozone , 1981 .

[33]  Yuk L. Yung,et al.  Vertical transport and photochemistry in the terrestrial mesosphere and lower thermosphere (50–120 km) , 1981 .

[34]  R. Cicerone,et al.  Photodissociation of isotopically heavy O 2 as a source of atmospheric O 3 , 1980 .

[35]  H. Levy,et al.  Three-Dimensional Tracer Structure and Behavior as Simulated in Two Ozone Precursor Experiments , 1980 .

[36]  M. Kurylo,et al.  Evidence for atom exchange in OH reactions with carbonyl compounds: 18OH+CO2 → 18OCO+OH; 18OH+CO → 18OC+OH , 1979 .

[37]  H. Singh.  Atmospheric halocarbons: Evidence in favor of reduced average hydroxyl radical concentration in the troposphere , 1977 .

[38]  D. Hunten,et al.  Spectroscopy and Acronomy of O2 on Mars , 1972 .

[39]  S. Wofsy,et al.  Atmospheric CH4, CO, and CO2 , 1972 .

[40]  M. Nicolet,et al.  The production of nitric oxide in the stratosphere by oxidation of nitrous oxide , 1972 .

[41]  M. McElroy,et al.  Nitrous Oxide: A Natural Source of Stratospheric NO , 1971 .

[42]  H. Levy.  Normal Atmosphere: Large Radical and Formaldehyde Concentrations Predicted , 1971, Science.

[43]  D. E. Milligan,et al.  Infrared Spectrum and Structure of the Species CO3 , 1971 .

[44]  W. Demore,et al.  Pressure dependence of carbon trioxide formation in the gas-phase reaction of O/D1/ with carbon dioxide , 1970 .

[45]  D. Hunten,et al.  Photochemistry of CO2 in the atmosphere of Mars , 1970 .

[46]  J. Noxon.  Optical Emission from O(1D) and O2(b 1Σg) in Ultraviolet Photolysis of O2 and CO2 , 1970 .

[47]  H. Craig,et al.  Oxygen isotope fractionation between CO2 and water, and the isotopic composition of marine atmospheric CO2 , 1968 .

[48]  M. McElroy.  The Upper Atmosphere of Mars , 1967 .

[49]  W. Breckenridge,et al.  Reaction of O(1D) with CO2 at Low Temperatures , 1967 .

[50]  S. Jaffe,et al.  Isotopic exchange reactions of atomic oxygen produced by the photolysis of NO2 at 3660 Å , 1966 .

[51]  D. L. Baulch,et al.  Isotopic exchange of O(1D) with carbon dioxide , 1966 .

[52]  R. Cvetanovic,et al.  Isotopic Exchange of the Excited Oxygen Atoms with CO218 and Their Collisional Deactivation , 1964 .

[53]  H. Taube,et al.  Some Photochemical Reactions of O3 in the Gas Phase , 1962 .

[54]  Charles D. Keeling,et al.  The concentration and isotopic abundances of carbon dioxide in rural and marine air , 1961 .