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Mauersberger, K.

Publications and source records attributed to Mauersberger, K..

At least 19 records

Ozone absorption spectroscopy in search of low-lying electronic states

A spectrometer capable of detecting ozone absorption features 9 orders of magnitude weaker than the Hartley band has been employed to investigate the molecule's near-infrared absorption spectrum. At this sensitivity a wealth of information on the low-lying electronically excited states often believed to play a role in atmospheric chemistry is available in the form of vibrational and rotational structure. We have analyzed these spectra using a combination of digital filtering and isotope substitution and find evidence for three electronically excited states below 1.5 eV. The lowest of these states is metastable, bound by approximately 0.1 eV and probably the (3)A2 rather than the (3)B2 state. Its adiabatic electronic energy is 1.24 +/- 0.01 eV, slightly above the dissociation energy of the ground state. Two higher states, at 1.29 +/- 0.03 and 1.48 +/- 0.03 eV are identified as the (3)B2 and the (3)B1, respectively. Combined with other recent theoretical and experimental data on the low-lying electronic states of ozone, these results imply that these are, in fact, the lowest three excited states; that is, there are no electronically excited states of ozone lying below the energy of O(3P) + O2((3)Sigma(-), v = 0). Some of the implications for atmospheric chemistry are considered.

Anderson, S. M.↗

Multi-isotope study of ozone - Implications for the heavy ozone anomaly

Laboratory experiments have been performed with O and O2 in their ground electronic states to study the distribution of all possible ozone isotopes formed. Results show that with respect to (O-48)3, the two symmetric molecules O-17O-17O-17 and O-18O-18O-18 are depleted, in good agreement with standard recombination theory. An enrichment of about 18 percent is found in the asymmetric molecule O-16O-17O-18, while all others carry about 2/3 of that. A comparison with past laboratory and stratospheric ozone isotope measurements shows a standard enrichment which resides in asymmetric molecules only, and leads to an enrichment of stratospheric (O-49)3 and (O-50)3 of 8-9 percent; this has been observed in recent balloon experiments. The enrichments in the stratosphere can reach 40 percent at certain altitudes. Only when ozone was formed in an electric discharge process have larger enrichments been measured in laboratory experiments, affecting both symmetric and asymmetric molecules.

Mauersberger, K.↗

Mass Spectrometric Measurement of Martian Krypton and Xenon Isotopic Abundance

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.

Mahaffy, P.↗

Oxygen isotope fractionation in stratospheric CO2

A new cryogenic collection system has been flown on board a balloon gondola to obtain separate samples of ozone and carbon dioxide without entrapping major atmospheric gases. Precision laboratory isotopic analysis of CO2 samples collected between 26 and 35.5 km show a mass-independent enrichment in both O-17 and O-18 of about 11 per mil above tropospheric values. Ozone enrichment in its heavy isotopes was 9 to 16 percent in O3-50 and 8 to 11 percent in O3-49, respectively (Schueler et al., 1990). A mechanism to explain the isotope enrichment in CO2 has been recently proposed by Yung et al. (1991). The model is based on the isotope exchange between CO2 and O3 via O(1D), resulting in a transfer of the ozone isotope enrichment to carbon dioxide. Predicted enrichment and measured values agree well.

Thiemens, M. H.↗

Near-infrared absorption spectra of (O-16)3 and (O-18)3 - Adiabatic energy of the 1A2 state?

The band positions and isotope shifts for the weak vibronic bands of O3 near 1 micron are determined experimentally using a low-resolution dual-beam absorption spectrometer with a 0.2-m holographic-grating monochromator and identical absorption chambers of volume about 600 cu cm and optical path length 46 cm. The experimental setup and procedures and the signal-processing methods applied are described, and the results are presented in tables and graphs. It is found that the adiabatic energy of the 1A2 state lies 9990 + or - 70/cm (1.24 + or - 0.01 eV) above the electronic ground state, close to the O + O2 dissociation limit. The applicability of the present results to studies of O3 in the upper atmosphere is indicated.

Anderson, S. M.↗

Measurement of isotopic abundances in collected stratospheric ozone samples

Enrichment of heavy O3 isotopes has been measured in collected stratospheric samples. A balloon-borne cryogenic sampler was used to gather six O3 samples between 26 and 35 km in three flights. Subsequent laboratory mass spectrometer analysis of rare O3 isotopes at both mass 49 and 50 has resulted in more precise measurements than have previously been reported with in situ and ground-based techniques. In one flight, (O-50)3 was enriched by 12-16 percent and (O-49)3 by 9-11 percent, both increasing with altitude. In the remaining two flights, the isotope enrichment was nearly mass-independent at 8-9 percent. The enrichments in O3 at mass 50 are less than the large 40 percent value observed in some stratospheric measurements but similar to (O-49)3 and (O-50)3 fractionations produced in laboratory-generated ozone.

Schueler, B.↗

Laboratory studies of heavy ozone

Dissociation of ozone in the Chappuis bands has been used as an O atom source to study isotope effects occurring in the O(3P) + O2(3 Sigma g) recombination reaction. The ozone produced was found to be enriched in both of its heavy isotopes. The pressure dependence (5-1000 torr) and temperature dependence (127-360 K) of this isotope effect have been investigated. The enrichment is approximately constant from 5 torr to 100 torr and decreases at higher pressures. It increases with temperature, with O3-50 showing a slightly faster rate of increase than O3-45. The results of this experiment have clearly isolated the source of the isotope effect to the gas phase O(3P) + O2(3 Sigma g) recombination reaction.

Morton, J.↗

Temperature dependence of the ozone absorption cross section at the 253.7-nm mercury line

The temperature dependence of the ozone absorption cross section at 253.7 nm has been measured between 195 and 351 K. The experimental technique employed circumvents the necessity to determine the absolute ozone concentration for each temperature measurement. Below 273 K the cross section increases approximately 0.6 percent, while toward higher temperatures the cross section decreases rapidly. In a comparison, good agreement with other recently made measurements is shown.

Barnes, J.↗

Upper limit on the rate constant for isotope exchange between molecular oxygen and ozone at 298 K

The gas phase bimolecular isotope exchange reaction between molecular oxygen and ozone has been investigated directly for the first time. Its rate coefficient is found to be less than 2 x 10 to the -25th cu cm/sec at 298 K, over six orders of magnitude below recent estimates. Much faster exchange was observed over condensed ozone at 77 K, suggesting isotopic scrambling is catalyzed under these conditions. The low rate coefficient implies that homogeneous exchange between ground state oxygen and ozone molecules cannot play a significant role in heavy ozone chemistry.

Anderson, S. M.↗

Precision ozone calibration system based on vapor pressures of ozone

A precision ozone calibration system for stratospheric research has been developed and evaluated. Vapor pressures above solid ozone are mixed with a carrier gas (N2) to produce stratospheric ozone mixing ratios at total pressures of 1 to cover 20 torr. The uncertainty in the ozone mixing ratios is approximately + or - 1.5 percent, the stability of ozone is + or - 0.3 percent. Experiments to be calibrated may sample the gas mixture over a wide range of flow rates; the maximum throughput of gas with corrections of less than 1 percent to ozone is about 200 torr 1/min. A mass spectrometer system continuously monitors the purity and stability of the N2-O3 gas mixture.

Mauersberger, K.↗

Ozone isotope measurements in the stratosphere

Mass spectrometer measurements of ozone made during two balloon flights included its heavy isotopes at mass 49 and 50. Both flights were flown during the day and during summer from Palestine, TX. At float altitudes above 42 km the enrichments in heavy ozone were 41 percent and 23 percent, respectively. The enrichment appears to be mass independent since, at high altitudes, both 49 and 50 show the same enhancement. During the descent the enrichment in heavy ozone decreased, faster during the first flight than during the second, reaching values between 15 and 20 percent above 30 km. Near and below this altitude another increase is observed. During a night flight, previously reported, an enhancement in heavy ozone of over 40 percent at 32 km was found, decreasing both toward higher and lower altitudes.

Mauersberger, K.↗

Measurement of the ozone absorption cross-section at the 253.7 nm mercury line

The absorption cross-section of ozone at 253.7 nm is frequently used as a standard for the entire UV wavelength range. The presently accepted value is 1.147 x 10 to the -17th/sq cm, which is known with an uncertainty of about 2 percent. The cross-section has been recently measured by simultaneously monitoring the ozone pressure, the impurities in the ozone gas, the gas temperature, and the UV beam intensity. The cross-section at room temperature was found to be 1.137 x 10 to the -17th/sq cm having an uncertainty of + or - .7 percent. The improved accuracy will aid a number of ozone experiments including the in situ photometers and Solar Backscatter Ultraviolet instruments.

Mauersberger, K.↗

Precision ozone vapor pressure measurements

The vapor pressure above liquid ozone has been measured with a high accuracy over a temperature range of 85 to 95 K. At the boiling point of liquid argon (87.3 K) an ozone vapor pressure of 0.0403 Torr was obtained with an accuracy of + or - 0.7 percent. A least square fit of the data provided the Clausius-Clapeyron equation for liquid ozone; a latent heat of 82.7 cal/g was calculated. High-precision vapor pressure data are expected to aid research in atmospheric ozone measurements and in many laboratory ozone studies such as measurements of cross sections and reaction rates.

Hanson, D.↗

A new ozone standard - The vapor pressure of ozone at liquid argon temperatures

The vapor pressure of ozone has been measured at liquid argon temperatures. At the normal boiling point of argon (-185.9 C) an ozone pressure of 0.0405 torr was obtained with an accuracy of + or - 1.5 percent. Increases and decreases in liquid argon temperatures raised and lowered the ozone vapor pressure, respectively. During the vapor pressure measurements the purity of ozone was monitored with a mass spectrometer. The proposed ozone standard will considerably improve the calibration of experiments for atmospheric research, the determination of absorption cross sections and other laboratory ozone studies.

Mauersberger, K.↗

Operation of a microchannel plate counting system in a mass spectrometer

A multiplier detector system has been developed as part of a mass spectrometer in an ion counting mode. During its operation ions striking a microchannel plate release pulses of electrons which are accelerated to a phosphor layer. The resulting flash of light is carried by a fiber-optic bundle to a photodiode array. The detector simultaneously counts ions throughout a mass spectrum covering more than 30 amu. It extends the mass spectrometer's operation toward low count rates for trace gas analysis. Each mass peak can be independently measured at count rates between 0.1 and 1000 counts/s. Higher rates on a few peaks do not blind the entire detector. The detector's capabilities have been demonstrated by measuring Kr and Xe isotopes in air at natural abundances. The mass spectrometer, detector, and readout electronics are sufficiently compact to permit use in a balloon-borne experiment.

Murphy, D. M.↗

The response of thermospheric atomic nitrogen to magnetic storms

Neutral composition data obtained by the open-source neutral-mass spectrometer on the polar orbiting Atmosphere Explorer D satellite during the periods October 31 to November 15, 1975, and January 5 to 15, 1976, are used to characterize the response of thermospheric atomic nitrogen densities to geomagnetic activity. These periods provided nearly simultaneous polar and low-latitude data coverage. At low and middle latitudes near dawn and at all latitudes on the dayside, N densities at 400 km appear to vary like those of a species of atomic mass 14: N is observed to increase with increasing geomagnetic activity in a manner similar to that of O. At auroral latitudes near dawn, however, there is a more complex dependence on the amplitude of the disturbance. For substorm-scale activity, N tends to increase during periods of auroral heating but exhibits a sharp temporary decrease afterward. During large storms there is a significant but short-lived increase of N at auroral latitudes. The present results support current models showing that N is produced and transported out of the auroral zone during geomagnetic disturbances.

Engebretson, M. J.↗

Mass spectrometry in the stratosphere

A gas expansion system incorporating a mass spectrometer that has been successfully flown in the stratosphere is described. Neutral gas particles are formed into a molecular beam that traverses the ion source of the mass spectrometer without wall interactions. It is noted that vertical profiles of such constituents as H2O, CO2, and O3 have been measured in the altitude range of 20 to 40 km during balloon descents. Isotopes of important gases (N2, O2, Ar) provided in-flight calibration standards. Before each flight the mass spectrometer system is calibrated in the laboratory for many gases of interest, including ozone. Mixing ratios of ozone established from recent flights have accuracies of better than 5 percent. The sensitivity of the system is sufficient to detect as well the heavy isotope of ozone at mass 50. A noticeable enhancement of heavy ozone in the upper stratosphere has been found. The mass spectrometer system is seen as providing a unique opportunity to perform in situ measurements in the stratosphere in combination with isotopic studies.

Mauersberger, K.↗

Measurement of heavy ozone in the stratosphere

The distribution of heavy ozone (molecular mass 50) has been measured for the first time in the stratosphere with a mass spectrometer system. During a balloon descent after midnight on September 4, 1980, a pronounced enhancement of heavy ozone was found. The maximum in the isotopic ratio, (O-18)(O-16)2/(O-16)3, occurred at 32 km where the enhancement of heavy ozone was over 40%. The ratio decreased toward higher and lower altitudes, and reached the standard value below 24 km. These measurements confirm an earlier prediction that there exists a preferred production mechanism for heavy ozone in the stratosphere.

Mauersberger, K.↗