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NASA NTRS2000

Measurement of ClO and CO2 for ACCENT

Observations have shown that ozone in largely removed in rocket plumes within an hour of launch [M.N. Ross, et al., Nature 390, 62-64, 1997]. Large abundances of chlorine oxide (ClO) were first detected in the fresh plume of a Delta rocket in May of 1998 from the NASA WB-57 during the Air Force RISO campaign by the CORE instrument developed at UC Irvine. Similar abundances were detected a month later in the plume of an ATLAS II rocket. Although the maximum ClO observed in these plumes was twenty-five times larger than the highest values ever observed in the perturbed polar vortices, in a new study, [M.N. Ross, et al., Geophys. Res. Lett., 2000, in press] could not account for observed ozone losses based on known chlorine photochemistry. New measurements were obtained in plumes of Delta, Atlas, and Athena rockets in 1999 during ACCENT with the CORE instrument augmented with a modified LiCor non-dispersed infrared detector for fast-response measurements of carbon-dioxide (CO2). The absolute abundance of this specie constrains the rocket emission stoichiometry, and its relative abundance serves as a tracer of dilution. The combination of ClO and CO2 will provide important new insights into the temporal and spatial evolution of reactive chlorine partitioning and its dependence on rocket motor type.

Toohey, Darin↗

NASA NTRS1999

The Coupling of ClONO2, ClO, and NO2 in the Lower Stratosphere From in Situ Observations Using the NASA ER-2 Aircraft

The first in situ measurements of ClONO2 in the lower stratosphere, acquired using the NASA ER-2 aircraft during the Polar Ozone Loss in the Arctic Region in Summer (POLARIS) mission, are combined with simultaneous measurements of ClO, NO2, temperature, pressure, and the calculated photolysis rate coefficient (J(sub ClONO2)) to examine the balance between production and loss of ClONO2. The observations demonstrate the ClONO2 photochemical steady state measurement, [ClONO2](sup PSS) = k[ClO][No2]/J(sub ClONO2), is in good agreement with the direct measurement, [ClONO2](sup MEAS). For the bulk of the data (80%), where T > 220 K and latitudes > 45 N, [ClONO2](sup PPS) = 1.15 +/- 0.36(1-sigma)[ClONO2](sup MEAS), while for T< 220 K and latitudes < 45 N, the result is somewhat less at 1.01 +/- 0.30. The cause of the temperature and/or latitude trend is unidentified. These results are independent of solar zenith angle and air density, thus there is no evidence in support of a pressure-dependent quantum yield for photodissociation of ClONO2 at wavelengths > 300 nm. These measurements confirm the mechanism by which active nitrogen (NOx = NO + NO2) controls the abundance of active chlorine (Clx = ClO + Cl) in the stratosphere.

Stimpfle, R. E.↗

NASA NTRS1977

Rate constant for formation of chlorine nitrate by the reaction ClO + NO2 + M

The pseudo-first-order decay of ClO in a large excess of NO2 was monitored in a discharge flow/mass-spectrometer apparatus in order to measure the rate constant of the reaction ClO + NO2 + M yields ClONO2 + M for M = He, Ar, and N2 over the temperature range from 248 to 417 K. Numerical results are given for He at 248, 299, 360, and 417 K (1 to 9 torr); for Ar at 298 K (1 to 4 torr); and for N2 at 299, 360, and 417 K (1 to 6 torr). Systematic errors are estimated, and identification of the reaction product is discussed. The results obtained are shown to be in excellent agreement with other recent measurements of the same rate constant.

Leu, M. T.↗

NASA NTRS1977

Reaction rates for O3 + HCl yielding O + O2 + HCl, Cl + O3 yielding ClO + O2, and HCl + O yielding OH + Cl at elevated temperatures

Ozone and a much greater quantity of hydrogen chloride, slightly diluted by oxygen and argon, were heated by a shock wave process to temperatures in the range 480-1300 K at pressures from four to eight atmospheres. From variations in ozone concentration, determined by the attentuation of 2537-A radiation, the rate coefficient for the reaction O3 + HCl yielding O + O2 + HCl was determined to be k1 = (4.0 plus or minus 1.5) x 10 to the minus 10 exp(-10,408/T)cm3/s for temperatures of 480-720 K. From the concentration of ClO remaining at the end of ozone decomposition the rate coefficients for the reactions Cl + O3 yielding ClO + O2 and HCl + O yielding OH + Cl were also deduced for a temperature of about 1100 K.

Park, C.↗

NASA NTRS1977

High resolution absorption cross sections for the A2Pi-X2Pi system of ClO

High-resolution ultraviolet absorption cross-sections for the ClO molecule are obtained, with the aim of facilitating studies of ozone depletion resulting from the injection of chlorofluorocarbons into the atmosphere. The spectroscopic analysis, which involves a frequency-doubled tunable dye laser with a bandwidth of 0.015 A, is described. Studies of the rotational lines of the ClO A 2Pi 3/2-X2Pi 3/2 9-10 band were conducted. Peak cross-sections for the P and R lines of the 9-0 band are found to be 10.0, 9.6, 8.6, 10.6, 10.3, and 9.2 times ten to the negative seventeenth power cm squared, with estimated accuracy of plus or minus 25%. Problems in distinguishing between Cl-35 and Cl-37 absorption are also considered.

Wine, P. H.↗

NASA NTRS1978

Calculated rate constants for the reaction ClO + O yields Cl + O2 between 220 and 1000 deg K

Classical trajectory calculations are presented for the reaction ClO + O yields Cl + O2, a reaction which is an important step in the chlorine-catalyzed destruction of ozone which is thought to occur in the 220 and 1000 K. The calculated rate constant is 4.36 x 10 to the minus 11th power exp (-191/T)cu cm molecule (-1)s(-1) and its value at 300 K is 2.3 plus or minus 10 to the 11th power cu cm molecule (-1)s(-1), about a factor of 2 lower than recent experimental data. The empirical potential energy surface used in the calculations was constructed to fit experimental data for ClO, O2 and ClOO molecules. Other important features of this potential surface, such as the barrier to reaction, were varied systematically and calculations were performed for a range of conditions to determine the best theoretical rate constants. Results demonstrate the utility of classical trajectory methods for determining activation energies and other kinetic data for important atmospheric reactions.

Jaffee, R. L.↗

NASA NTRS1977

Theoretical intensity parameters for the vibration-rotation bands of ClO

Intensity parameters for the vibration-rotation bands of ClO were calculated by evaluating matrix elements of the vibrational eigenfunctions using the theoretical dipole moment curve. These vibrational eigenfunctions are based on realistic Klein-Dunham potentials deduced from experimental values (Coxon et al, 1976) for certain vibrational energy levels. The data can be applied to the interpretation of remote or in situ experiments to deduce stratospheric ClO concentrations from vibration-rotation absorption spectra.

Langhoff, S. R.↗

NASA NTRS1979

Rate constants for the reactions of OH with ClO, Cl2, and Cl2O at 298K

Recent concern about the depletion of stratospheric ozone by chlorine species from the decomposition of chlorofluoromethanes has emphasized the need for laboratory studies of the first reaction steps involved, especially those which control the concentration of the OH and ClO radicals in the stratosphere. Rate constants for the reactions of OH with ClO, Cl2, and Cl2O at 298 K have been determined in a discharge flow system using resonance fluoresence detection. The results are (9.1 + or - 1.3) x 10 to the -12th, (5.5 + or - 0.3) x 10 to the -14th, and (6.5 + or - 0.5) x 10 to the -12th (all in units of cu cm/sec), respectively.

Leu, M. T.↗

NASA NTRS1979

An explanation of the preferential formation of less stable isomers in three-body reactions - Cl + NO2 + M; ClO + NO2 + M

A realistic assessment of the potential depletion of stratospheric ozone due to manmade emissions requires a knowledge of the sources and sinks of the potential threat. The reactions ClO + NO2 + M yield products and Cl + NO2 + M yield products are of interest because they represent possible sink mechanism for both odd chlorine and odd nitrogen species. In this paper, the Troe method (1977) is used to calculate the low-pressure limit rate constants of the above three-body reactions. The result for the Cl + NO2 + M reaction is found to be in excellent agreement with the experimental finding of Niki et al. (1978), where both nitryl chloride and chlorine nitrate are products of the cited reaction. An explanation is proposed to account for apparent discrepancy between the measured rate constants for ClO + NO2 + M in the forward and reverse directions. Stratospheric implications are also discussed.

Chang, J. S.↗

NASA NTRS1980

Product distribution for the reaction of HO2 with ClO

The paper reports the direct measurement of the reaction product HOCl from the reaction of H2O with ClO, and sets an upper limit for the possible product O3, using a discharge flow/mass spectrometry/resonance fluorescence apparatus. The upper limits of the reaction channel producing HCl + O3 are 1.5% at 298 K and 3.0% at 248 K. It is seen that the HCl production rate from the HO2 + ClO reaction could be as large as that from the Cl + CH4 reaction in the lower and middle stratosphere. Thus, this reaction may possibly increase the HCl production rate appreciably and thereby reduce the calculated O3 destruction by chlorofluoromethanes.

Leu, M.-T.↗

NASA NTRS1985

Stratospheric ClO - In-situ detection with a new approach

Stratospheric chlorine monoxide concentrations were measured in situ using a new and improved observational method in which the detection package is lowered on a tether from a balloon-borne platform floating near 40 km altitude and then reeled back up. Two reel down and reel up sequences covering 38 to 31 km produced (ClO) profiles which agree with each other to + or - 12 percent. The measured (ClO) profile falls within the envelope of nine previous fast parachute drop results, but exhibits a different shape, peaking near 32 km as opposed to approximately 39 km for the average of the previous profiles. These results are lower than but consistent with the profiles derived from remote sensing methods, and indicate the need for simultaneous measurements of relevant species.

Brune, Wm. H.↗

NASA NTRS1986

In situ observations of midlatitude stratospheric ClO and BrO

A balloon-borne experiment to measure midlatitude stratospheric BrO and ClO concentrations by NO chemical conversion/atomic resonance fluorescence was flown from Palestine, Texas, on May 20 1986. In this first study of BrO, no signal attributable to BrO was detected, and upper limits (2 sigma uncertainty) between 35 and 24 km altitude give BrO mixing ratios less than 15 pptv. Current models predict mixing ratios that are 1.7 times larger. Measurements of ClO were obtained at less than 0.2-km altitude resolution from 41 to 22 km. The smoothly varying altitude profile lies within the range of two-dimensional model calculations.

Brune, William H.↗

NASA NTRS1988

Midlatitude ClO below 22 km altitude - Measurements with a new aircraft-borne instrument

Midlatitude stratospheric ClO at altitudes below 22 km has been measured for the first time. Measurements were made at latitudes between 27 and 48 deg N during three flights from Moffett Field, CA, in June and July of 1987, with a new instrument flown on the NASA ER-2 aircraft. The result from these flights is that the ClO mixing ratio increases from less than 0.5 pptv at 16.8 km to 2.0 pptv at 18.3 km and 10.1 pptv at 21 km. These altitude profiles agree with an extrapolated profile from a May 1986 balloon-borne experiment (Brune and Anderson, 1986).

Brune, Wm. H.↗

NASA NTRS1988

Formation of the Antarctic ozone hole by the ClO dimer mechanism

New measurements of the low-altitude ClO profile, made during September 1987, are presented along with detailed observations of ozone depletion over McMurdo Station, Antarctica during the same period. The results show that both the rate and altitude range of ozone depletion can be quantitatively accounted for by a mechanism in which the ClO dimer is the important intermediary in the catalytic destruction of ozone. An alternative bromine mechanism appears capable of contributing only 5-15 percent to the ozone loss rate.

Barrett, J. W.↗

NASA NTRS1989

Infrared line intensity measurements in the v = 0-1 band of the ClO radical

Integrated line intensity measurements in the ClO-radical fundamental vibrational v = 0-1 band were carried out using a high-resolution Fourier transform spectrometer coupled to a long-path-length absorption cell. The results of a series of measurements designed to minimize systematic errors, yielded a value of the fundamental IR band intensity of the ClO-radical equal to 9.68 + or - 1.45/sq cm per atm at 296 K. This result is consistent with all the earlier published results, with the exception of measurements reported by Kostiuk et al. (1986) and Lang et al. (1988).

Burkholder, James B.↗

NASA NTRS1989

Ozone destruction by chlorine radicals within the Antarctic vortex - The spatial and temporal evolution of ClO-O3 anticorrelation based on in situ ER-2 data

The chemical evolution of the Antarctic vortex region was studied during August 23-September 22, 1987 on the basis of in situ O3 and ClO data collected by the ER-2 aircraft. Particular attention is given to the evolution of the ClO-O3 anticorrelation from the first flight on August 23, 1987, which penetrated well into the vortex, through the course of 10 flights culminating on September 22, 1987. It is concluded that the disappearance of ozone within the Antarctic vortex results from halogen-catalyzed recombination of O3 to molecular oxygen.

Anderson, J. G.↗

NASA NTRS1989

Kinetics and product studies of the reaction ClO + BrO using discharge-flow mass spectrometry

The kinetics and product branching ratios of the reaction between ClO and BrO were studied at 1 torr pressure over the temperature range 220-400 K, using the method of discharge-flow mass spectrometry. Three product channels were identified and quantified: Br + ClOO, Br + OClO, and BrCl + O2, indicating that the reaction mechanism of ClO + BrO involves metastable intermediates. The overall reaction rate coefficient and the rate coefficients for the three channel reactions are given.

Friedl, Randall R.↗

NASA NTRS1990

In situ observations of ClO in the Arctic Stratosphere - ER-2 aircraft results from 59 deg N to 80 deg N latitude

Large abundances of ClO were observed inside the Arctic polar vortex during 14 flights of the NASA ER-2 aircraft from Stavanger, Norway (59 deg N, 6 deg E) to 80 deg N latitude. Flights were conducted at altitudes between 14 and 20 km when the solar zenith angle was between 79 and 101 deg. Data are reported for three flights that represent the main features observed during the mission. These data, comparable to those obtained in the Antarctic ozone hole, indicate that the springtime Arctic polar vortex was extensively perturbed by heterogeneous chemistry and contained enough ClO to catalytically destroy ozone rapidly.

Brune, W. H.↗