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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
NASA NTRS1984

Measurement of H2O and other trace gases in the stratosphere using a high resolution far-infrared spectrometer at 28 km

Data analysis results from the 1983 BIC 1 and 2 balloon flights are presented, with emphasis on H2O2, OH, HCL, O3, O2, and H2O. A 2 sigma limit on H2O2 abundance was set, as a function of altitude. This is comparable to or less than the theoretically predicted winter abundances from the 2-D models of Dupont, with a large enough summer maximum to facilitate concentration profile measurements. There is a definite drop in OH concentration from day to night following two model profiles. There was general agreement between HF measurements. The dominant role of the far wings of H2O lines in low altitude spectra was recognized. The strength of these wings exceeds that of many molecular line cores, including O3 and O2, especially near the long wavelength end of the spectra (100 cm (-1)). Newly measured positions for O3 and H2O were obtained.

Traub, W. A.↗
NASA NTRS1983

Kinetics and mechanism of the oxidation of S(IV) by ozone in aqueous solution with particular reference to SO2 conversion in nonurban tropospheric clouds

Results are presented from a laboratory study of the kinetics of the S(IV)-O3 reaction in aqueous solution, including measurements of the effects of UV radiation, dissolved transition metals, and an antioxidant (hydroquinone) on the rate. On the basis of the results, relative rates of S(IV) conversion by O3 in tropospheric cloud water are compared with those predicted for H2O2 and for O2. The reaction mechanism is discussed, with an outline given of the elements of a possible reaction scheme. Application of the rate constants obtained to SO2 conversion in cloud water predicts conversion rates by ozone to be competitive with those by H2O2 at pH above about 4.5 and to dominate at pH above about 5.5. It is pointed out that since these pH's are typical for nonurban tropospheric cloud water, ozone is a potentially important contributor to the overall oxidative conversion of SO2 to sulfate in the nonurban troposphere.

Maahs, H. G.↗
NASA NTRS1984

Chemical kinetic reaction mechanism for the combustion of propane

A detailed chemical kinetic reaction mechanism for the combustion of propane is presented and discussed. The mechanism consists of 27 chemical species and 83 elementary chemical reactions. Ignition and combustion data as determined in shock tube studies were used to evaluate the mechanism. Numerical simulation of the shock tube experiments showed that the kinetic behavior predicted by the mechanism for stoichiometric mixtures is in good agrement with the experimental results over the entire temperature range examined (1150-2600K). Sensitivity and theoretical studies carried out using the mechanism revealed that hydrocarbon reactions which are involved in the formation of the HO2 radical and the H2O2 molecule are very important in the mechanism and that the observed nonlinear behavior of ignition delay time with decreasing temperature can be interpreted in terms of the increased importance of the HO2 and H2O2 reactions at the lower temperatures.

Jachimowski, C. J.↗
NASA NTRS1984

A measurement of the vibrational band strength for the v3 band of the HO2 radical

Laboratory measurements of the v(3) band strength of HO2 using a tunable diode laser to measure the absorption strength of a vibration-rotation line in the P branch near 1080/cm are reported. The HO2 is generated in a discharge-flow system by reaction of fluorine atoms with excess H2O2: F + H2O2 - HO2 + HF. The HO2 concentration is determined from measurements of F-atom concentrations using both chemical titration with Cl2 and tunable diode laser absorption by the F-atom spin-orbit transition near 404/cm. The experimental data are consistent with a value of k(3) = (1.6 + or - 0.3) x 10 to the 12th cu cm/s and a ratio k(4)/k(1) = 1.0 + or - 0.4. The line strength for the 6(15) - 7(16)F(1) transition is 2.9 x 10 to the -21 sq cm/molecule/cm, which corresponds to a v(3) band strength of 35 + or - 9/sq cm/(STP atm). This value is a factor of 1.6 to 6 lower than previous ab initio calculations.

Zahniser, M. S.↗
NASA NTRS1984

The photochemistry of a remote marine stratiform cloud

The coupled gas- and aqueous-phase photochemistry of a stratiform cloud in a remote region of the marine atmosphere is investigated with a time-dependent box model. Both scavenging of ambient acidic aerosols and gases as well as aqueous-phase chemical reactions within droplets are found to be important sources of acidity to cloud water and can lead to pH levels in cloud water in the remote marine atmosphere well below 5.6. The major sources of acidity via aqueous-phase chemical reactions are the generation of sulfuric acid from dissolved SO2 and the generation of formic acid from dissolved formaldehyde. In both cases, aqueous-phase free radicals can play a significant role either directly by oxidizing dissolved SO2 and HCHO or indirectly by producing the aqueous-phase oxidant H2O2. The rate of SO2 conversion to sulfuric acid is sensitive to a variety of parameters including the accommodation or sticking coefficient for SO2, H2O2, HO2, and OH, the liquid water content, and the ambient levels of SO2, HNO3, and other acidic or basic gases. Because high levels of SO2 tend to deplete cloud water of H2O3, the possibility exists that the pH of precipitation in polluted regions will respond nonlinearly to reduced SO2 emissions.

Chameides, W. L.↗
NASA NTRS1984

The evolution of the prebiotic atmosphere

One-dimensional radiative-convective and photochemical models are used to estimate the vertical temperature structure and composition of the earth's prebiotic atmosphere. Greatly enhanced CO2 levels (100-1000 times present) are required to keep the mean surface temperature above freezing in the face of decreased solar luminosity during the earth's early history. Such high CO2 partial pressures would have affected the atmospheric oxidation state by facilitating the photochemical production of soluble species including H2O2 and H2CO. Oxidation of ferrous iron in the oceans by H2O2 dissolved in rainwater should have kept the atmospheric H2 mixing ratio above 0.0002, and the ground-level O2 mixing ratio below 10 to the -11th, regardless of the magnitude of the rate of volcanic release of reduced gases.

Kasting, J. F.↗
NASA NTRS1985

A measurement of the vibrational band strength for the upsilon sub 3 band of the HO2 radical

The HO2 radicals generated in a discharge-flow system were observed with tunable diode laser absorption in the P-branch of the nu(3) vibrationall band at 1080/cm. The observed line positions agree with those calculated from the molecular constants for the nu(3) bland obtained from a previous study using laser magnetic resonance spectroscopy. The band strength was determined by observing line center absoptions when HO2 is produced in the reaction F + H2O2 yields HO2 + HF (k1) with a measured concentration of atomic fluorine and excess hydrogen peroxide. F-atom concentrations are measured by diode laser absorption of the spin-orbit transition at 404/cm. The analysis accounts for HO2 losses due to the reactions of HO2 + HO2 yields H2O2 + O2 (k3) and F + HO2 yields HF + O2 (k4). The line strength for the 6(15) 7(16) F(1) transition is 2.9 x 10 to the 21st power sq cm/molecule/cm which corresponds to a nu(3) band strength of 34 +/- 9 sq/cm(STP atm). This value is a factor of 6 lower than previous ab initio calculations. These results will be useful in assessing the feasibility of atmospheric measurements of HO2 using infrared absorption techniques.

Zahniser, M. S.↗
NASA NTRS1984

Importance of formaldehyde in cloud chemistry

A physical-chemical model which is an extension of that of Hong and Carmichael (1983) is used to investigate the role of formaldehyde in cloud chemistry. This model takes into account the mass transfer of SO2, O3, NH3, HNO3, H2O2, CO2, HCl, HCHO, O2, OH and HO2 into cloud droplets and their subsequent chemical reactions. The model is used to assess the importance of S(IV)-HCHO adduct formation, the reduction of H2O2 by HCHO, HCHO-free radical interactions, and the formation of HCOOH in the presence of HCHO in cloud droplets. Illustrative calculations indicate that the presence of HCHO inhibits sulfate production rate in cloud droplets. The direct inhibition of sulfate production rate in cloudwater due to nucleophilic addition of HSO3(-) to HCHO(aq) to form hydroxymethanesulfonate is generally low for concentrations of HCHO typical of ambient air. However, inhibition of sulfate production due to formaldehyde-free radical interactions in solution can be important. These formaldehyde-free radical reactions can also generate appreciable quantities of formic acid.

Adewuyi, Y. G.↗
NASA NTRS1985

Trapped Xe components in etched samples of the Murray (C2) and Murchison (C2) carbonaceous chondrites

Xe isotopic measurements are described. The samples analyzed were bulk chips of the Murray (C2) and Murchison (C2) carbonaceous chondrites that had been freeze-thaw disaggregated, etched with H2O2, and then split into colloidal and noncolloidal fractions using methanol. The etching removed a substantial portion of the trapped Xe and increased variations in measured isotopic ratios compared with bulk sample analyses. The Murray samples appeared to contain a binary mixture of U-Xe and H+L-Xe. The Murchison data concur with the Murray data for the heavy isotopes, but the structure at the light isotopes is obscured by spallation Xe. There is no evidence in these data for the separability of H-Xe and L-Xe. The fact that H2O2 etching removes Xe without prior demineralization supports the view that the carrier of a substantial portion of trapped Xe may reside on grain surfaces.

Jones, C. M.↗
NASA NTRS1985

Photochemical consequences of enhanced CO2 levels in earth's early atmosphere

Greatly enhanced atmospheric CO2 concentrations are the most likely mechanism for offsetting the effects of reduced solar luminosity early in the earth's history. CO2 levels of 80 to 600 times the present value could have maintained a mean surface temperature of 0 C to 15 C, given a 25 percent decrease in solar output. Such high CO2 levels are at least qualitatively consistent with the present understanding of the carbonate-silicate geochemical cycle. The presence of large amounts of CO2 has important implications for the composition of the earth's prebiotic atmosphere. The hydrogen budget of a high-CO2 primitive atmosphere would have been strongly influenced by rainout of H2O2 and H2CO. The reaction of H2O2 with dissolved ferrous iron in the early oceans could have been a major sink for atmospheric oxygen. The requirement that this loss of oxygen be balanced by a corresponding loss of hydrogen (by escape to space and rainout of H2CO) implies that the atmospheric H2 mixing ratio was greater than 2 x 10 to the -5th and the ground level O2 mixing ratio was below 10 to the -12th, even if other surface sources of H2 were small. These results are only weakly dependent on changes in solar UV flux, rainout rates, and vertical mixing rates in the primitive atmosphere.

Kasting, J. F.↗
NASA NTRS1985

Yields of O2(b 1 Sigma g +) from reactions of HO2

The production of O2(b 1 Sigma g +) has been monitored for several reactions of the HO2 radical at 300 K using a discharge-flow apparatus with resonance fluorescence and chemiluminescence detection. In all cases, the resulting quantum efficiencies were found to be less than 0.03. O2(b) was observed when F atoms were added to H2O2 in the gas phase. The signal strengths of O2(b) were proportional to initial concentrations of HO2 formed by the F + H2O2 reaction. Observed /O2(b)/, /HO2/, and /OH/ vs /F/0 were analyzed using a simple three-step mechanism and a more complete computer simulation with 22 reaction steps. The results indicate that the F + HO2 reaction yields O2(b) with an efficiency of (3.6 + or - 1.4) x 10 to the -3rd. Yields from the O + OH2 reaction were less than 0.02, indicating that this reaction cannot be a major source of the O2(b) emission observed in the earth's nightglow.

Keyser, L. F.↗
NASA NTRS1986

Tunable-diode laser absorption spectrometry

Tunable-diode laser absorption spectrometry (TDLAS) affords a number of advantages for atmospheric measurements. It is a universal method, applicable, in principle, to all gases of atmospheric interest. Because of its extremely high spectral resolution it provides unequivocal identification of the target species, with no interferences from other gases. It provides real-time, in situ measurements with time resolutions better than 1 minute. The sensitivity of the current TDLAS system is marginally capable of measuring HO2. This species exists in the troposphere at concentrations which are up to 2 orders of magnitude higher than those of HO and, in addition, is much less susceptible to removal by the surfaces of the instrument and its sampling system. HO2 is an important HO sub x species in its own right but can also give direct information on the HO concentration by virtue of the rapid partitioning between these two species. The addition of the high-frequency modulation technique to the TDLAS system would ensure its ability to measure HO2 under most atmospheric conditions. The ability of the TDLAS to measure hydrogen peroxide (H2O2) in the ambient atmosphere was also demonstrated. H2O2 measurements give a clear indication of HO sub x mixing ratios and are also important as a photolytic source of HO and as an important oxidant for other atmospheric consitituents such as SO2.

Schiff, H. I.↗
NASA NTRS1987

Evidence for stratospheric hydrogen peroxide

A statistically significant measurement of H2O2 in the stratosphere has been obtained. The results were obtained from the 112.19/cm RQ5 branch of the torsional-rotational spectrum with a remote-sensing far-infrared Fourier transform spectrometer during the Balloon Intercomparison Campaign (BIC-2), on June 20, 1983. The concentration above the balloon gondola is unexpectedly large, corresponding to 0.68 + or - 0.21 parts per billion by volume (ppbv) at an effective altitude of 38.3 km. Below the gondola altitude the concentration of H2O2 is slightly less than expected from the model predictions at 33.2 km (0.19 + or - 0.05 ppbv) and significantly less than expected at 29.3 km (0.08 + or - 0.03 ppbv).

Chance, K. V.↗
NASA NTRS1988

OH(A-X) fluorescence from photodissociative excitation of HO2 at 157.5 nm

The OH(A-X) fluorescence from photodissociative excitation of HO2 by F2 laser photons (157.5 nm) was observed and compared with the OH fluorescence spectra of H2O2 and the O2+CH3OH mixture. The rotational population distributions of OH(A) were obtained from the fluorescence spectra. The most populated levels are J = 4 for photodissociative excitation of HO2, J = 20 for H2O2, and J = 21 for the O2+CH3OH mixture. The fluorescence from the gas mixture is attributed to the O + H recombination for which the atoms are produced from photodissociation of parent molecules.

Suto, M.↗
NASA NTRS1987

Acid dew and the role of chemistry in the dry deposition of reactive gases to wetted surfaces

A formalism is developed to describe the dry deposition of soluble reactive gases to wetted surfaces in terms of the relevant meteorological conditions, the surface roughness, the total amount of liquid water present on the surface, the rate of accumulation of this water, and the species' solubility and reactivity in the surface water. This formulation is then incorporated into a model designed to simulate the generation of acidic dew from the deposition of HNO3, SO2, S(IV) oxidants, H2O2, and O3. Similar to the observations of dew in the continental U.S., the model generates a dewdrop pH of about 4 by the end of the night; the pH can rapidly fall to toxic levels due to rapid evaporation after sunrise. Relatively low deposition velocities are predicted for the SO2 and O3 because of their lower solubilities and hence larger surface resistances than those of the other oxidants. Because the chemical lifetime of the SO2 in the dew is influenced by the atmospheric levels of H2O2, O3, and SO2, the SO2 deposition velocity is a strong function of these species' atmospheric abundances.

Chameides, William L.↗
NASA NTRS1990

Simultaneous, in situ measurements of OH, HO2, O3, and H2O - A test of modeled stratospheric HO(x) chemistry

Simultaneous, in situ measurements of OH, HO2, H2O, and O3 from 37-23 km are reported. The partitioning between OH and HO2 and the total HO(x) concentration are compared with expected steady-state values. The ratio of HO2 to OH varies from less than 2 at 36 km to more than 3 at 25 km; in the lower stratosphere this ratio is nearly a factor of two less than predicted. The data are used to calculate HO(x) production and loss rates. The measured HO(x) mixing ratio is consistent with production dominated by the reaction of O(1D) with H2O, and loss controlled by NOy below 28 km and HO(x) above 30 km. The steady-state concentration of H2O2 is inferred from the measured HO2 concentration and calculated photolysis rate. The maximum H2O2 mixing ratio (at 33 km) is predicted to be less than 0.2 ppb.

Wennberg, P. O.↗
NASA NTRS1992

The oxidizing capacity of the earth's atmosphere - Probable past and future changes

A number of critical atmospheric chemical problems depend on the earth's oxidizing capacity, which is essentially the global burden of oxidants in the lower atmosphere. There is limited direct evidence for changes in the earth's oxidizing capacity since recent preindustrial times when, because of industrial and poulation growth, increasing amounts of O3 precursor trace gases (carbon monoxide, nitrogen oxides, and hydrocarbons) have been released into the atmosphere. The concentrations of O3 and possibly H2O2 have increased over large regions. Models predict that tropospheric O3 will increase about 0.3-1.0 percent per year over the next 50 years with both positive and negative trends possible for OH and H2O2. Models and the observational network for oxidants are improving, but validation of global models is still at an early stage.

Thompson, Anne M.↗
NASA NTRS1994

Measurement of atmospheric OH by titration of near-IR fluorescent dyes

Recent research has shown that certain polymethine dyes can be detected at ultratrace levels (greater than or equal to 6x10(exp -14) M) in solution by fluorimetry. These detection limits are possible because of the inherent sensitivity of fluorescence techniques, because the dyes fluoresce in the near infrared region where background interference is negligible, and because powerful infrared diode lasers are now available to improve the signal to noise ratio. Other work has shown that the hydroxyl radical destroys the ability of polymethine dyes to fluoresce. These observations form the basis for a new hydroxyl radical detector that is essentially a fluorometric titrator. Theoretically, the detector should show an acceptable sensitivity and response time. Assuming that the atmospheric HO concentration is about 10(exp -11) moles m(exp -3) (i.e. 10(exp 6) molecules cm(exp -3)), then 10 L of air 'titrated' with 20 mL of 10(exp -11) M dye solution (an easily detected concentration) should result in a drop in the fluorescent signal of 50 percent - a readily detectable change. At a flow rate of 3 L min(exp -1) the sampling time would be 3 minutes. The biggest potential problem is selectivity: other oxidants may also cause the fluorescence signal to be lost. The chemistry of polymethine dyes has not been studied in detail and so no quantitative data are available. However, a survey of the literature suggests that in general HO should react up to six orders of magnitude faster than HO2 and other radicals such as RO2 and RO. It should also react much more rapidly than H2O2 and O3. Thus it may be possible to discriminate kinetically against potential interfering substances. It was shown in the laboratory that 10(exp -4) M H2O2 has little effect on the absorption spectrum of the dye IR125 over a period of hours but that the band at 780 nm is slowly lost in water over a period of days even under argon in the dark. By contrast, DMSO solutions of IR125 are stable.

Betterton, Eric A.↗