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Carbon, hydrogen and nitrogen isotopes in solvent-extractable organic matter from carbonaceous chondrites

CCl4 and CH3OH solvent extractions were performed on the Murray, Murchison, Orgueil and Renazzo carbonaceous chondrites. Delta-D values of +300-+500% are found in the case of the CH3OH-soluble organic matter. The combined C, H and N isotope data makes it unlikely that the CH3OH-soluble components are derivable from, or simply related to, the insoluble organic polymer found in the same meteorites. A relation between the event that formed hydrous minerals in CI1 and CM2 meteorites and the introduction of water- and methanol-soluble organic compounds is suggested. Organic matter soluble in CCl4 has no N, and delta-C-13 values are lower than for CH3OH-soluble phases. It is concluded that there either are large isotopic fractionations for carbon and hydrogen between different soluble organic phases, or the less polar components are partially of terrestrial origin.

Becker, R. H.

Continental sources of halocarbons and nitrous oxide

Estimates of continental sources of CFC-11, CFC-12, CCl4, CH3CCl3 and N2O are derived from the atmospheric lifetime experiment in Adrigole, Ireland, and anthropogenic emissions of CCl4 and N2O from Europe have been identified. Relative source strengths are consistent with global budgets for the halocarbons and N2O. Different industrial release patterns for halocarbons are observed for Europe, the western United States and Australia.

Prather, M. J.

European sources of halocarbons and nitrous oxide - Update 1986

New information on seasonal and secular trends in the releases of CFCl3, CF2Cl2, CCl4, CH3CCl3, and N20 from Europe was obtained as part of the Atmospheric Lifetime Experiment. Semicontinuous measurements of these pollutants were made at Adrigole, Ireland, using lean air from the Atlantic Ocean as a baseline. The results obtained include unambiguous evidence for elevated levels of N2O occurring concurrent with halocarbon pollution events; the detection of trends in the relative emission of different halocarbons; the discovery of seasonal variations in emission of CF2Cl2, CCl4, and CH3Cl3; the characterization of typical summer and winter pollution episodes; and the identification of weather patterns over Europe that are associated with high concentrations of chlorofluorocarbons at Adrigole. It was estimated that the European source of N2O represents 25 percent of the global emissions associated with combustion and 10 percent of the integrated stratospheric losses.

Prather, Michael

Thermal emission spectroscopy of the middle atmosphere

The general objective of this research is to obtain, via remote sensing, simultaneous measurements of the vertical distributions of stratospheric temperature, ozone, and trace constituents that participate in the catalytic destruction of ozone (NO(sub y): NO, NO2, NO3, HNO3, ClONO2, N2O5, HNO4; Cl(sub x): HOCl), and the source gases for the catalytic cycles (H2O, CH4, N2O, CF2Cl2, CFCl3, CCl4, CH3Cl, CHF2Cl, etc.). Data are collected during a complete diurnal cycle in order to test our present understanding of ozone chemistry and its associate catalytic cycles. The instrumentation employed is an emission-mode, balloon-borne, liquid-nitrogen-cooled Michelson interferometer-spectrometer (SIRIS), covering the mid-infrared range with a spectral resolution of 0.020 cm(exp -1). Cryogenic cooling combined with the use of extrinsic silicon photoconductor detectors allows the detection of weak emission features of stratospheric gaseous species. Vertical distributions of these species are inferred from scans of the thermal emission of the limb in a sequence of elevation angles. The fourth SIRIS balloon flight was carried out from Palestine, Texas on September 15-16, 1986 with 9 hours of nighttime data (40 km). High quality data with spectral resolution 0.022 cm(exp -1), were obtained for numerous limb sequences. Fifteen stratospheric species have been identified to date from this flight: five species from the NO(sub y) family (HNO3, NO2, NO, ClONO2, N2O5), plus CO2, O3, H2O, N2O, CH4, CCl3F, CCl2F2, CHF2Cl, CF4, and CCl4. The nighttime values of N2O5, ClONO2, and total odd nitrogen have been measured for the first time, and compared to model results. Analysis of the diurnal variation of N2O5 within the 1984 and 1986 data sets, and of the 1984 ClONO2 measurements, were presented in the literature. The demonstrated ability of SIRIS to measure all the major NO(sub y) species, and therefore to determine the partitioning of the nitrogen family over a continuous diurnal cycle, is a powerful tool in the verification and improvement of photochemical modeling.

Kunde, V. G.

A Comparison of Measurements from ATMOS and Instruments Aboard the ER-2 Aircraft: Halogenated Gases

We compare volume mixing ratio profiles of N2O, CFC-11, CFC-12, CCl4, SF6, and HCl in the mid-latitude lower stratosphere measured by the ATMOS Fourier transform spectrometer on the ATLAS-3 Space Shuttle Mission with in situ measurements acquired from the NASA ER-2 aircraft during Nov. 1994. Good agreement is found between ATMOS and in situ correlations of [CFC-11], [CFC-12], and [SF6] with [N2O]. ATMOS measurements of [CCl4] are 15% high compared to ER-2 data, but agree within the systematic uncertainties. ATMOS observations of [HCl] vs [N2O] are within approximately 10% of ER-2 data for [HCl] > 1 ppbv, but exceed in situ measurements by larger fractional amounts for smaller [HCl]. ATMOS measurements of [ClONO2] agree well with values inferred from in situ observations of [ClO], [NO], and [O3]. The sum of [HCl] and [ClONO2] observed by ATMOS, supplemented by a minor contribution from [ClO] estimated with a photochemical model, is consistent with the levels of inorganic chlorine inferred from in situ measurements of chlorine source gases.

Chang, A. Y.

A Model Study of the Impact of Source Gas Changes on the Stratosphere for 1850-2100

The long term stratospheric impacts due to emissions of CO2, CH4, N2O, and ozone depleting substances (ODSs) are investigated using an updated version of the Goddard two-dimensional (2D) model. Perturbation simulations with the ODSs, CO2, CH4, and N2O varied individually are performed to isolate the relative roles of these gases in driving stratospheric changes over the 1850-2100 time period. We also show comparisons with observations and the God- 40 dard Earth Observing System chemistry-climate model simulations for the time period 1970-2100 to illustrate that the 2D model captures the basic processes responsible for longterm stratospheric change. The 2D simulations indicate that prior to 1940, the 45 ozone increases due to CO2 and CH4 loading outpace the ozone losses due to increasing N2O and carbon tetrachloride (CCl4) emissions, so that ozone reaches a broad maximum during the 1920s-1930s. This preceeds the significant ozone depletion during approx. 1960-2050 driven by the ODS loading. During the latter half of the 21st century as ODS emissions diminish, CO2, N2O, and CH4 loading will all have significant impacts on global total ozone based on the IPCC AIB (medium) scenario, with CO2 having the largest individual effect. Sensitivity tests illustrate that due to the strong chemical interaction between methane and chlorine, the CH4 impact on total ozone becomes significantly more positive with larger ODS loading. The model simulations also show that changes in stratospheric temperature, Brewer-Dobson circulation (BDC), and age of air during 1850-2100 are controlled mainly by the CO2 and ODS loading. The simulated acceleration of the BDC causes the age of air to decrease by approx. 1 year from 1860-2100. The corresponding photochemical lifetimes of N2O, CFCl3, CF2Cl2, and CCl4 decrease by 11-13% during 1960-2100 due to the acceleration of the BDC, with much smaller lifetime changes 4%) caused by changes in the photochemical loss rates.

Fleming, E. L.

Tetraperchlorate of methane

The preparation of the tetraperchlorate of methane (TPM) was attempted. Displacement of halogen from carbon tetrahalides was accomplished with either CCl4 or CBr4 using the halogen perchlorates, ClOClO3, and BOClO3. Although the displacement process was successful, the generated carbon perchlorate intermediates were not isolated. Instead, these species decomposed to COCl2, CO2, and Cl2O7. The vigorous displacement reaction that often occurred required moderation. Fluorocarbon solvents and chlorine perchlorate were successfully tested for compatibility, permitting their use in these synthetic reactions. While the sought for moderating effect was obtained, the net result of the displacement of halogen from CX sub 4 substrates was the same as before. Thus only CO2, COCl2, and Cl2O7 were isolated.

Schack, C. J.

Application of selected methods of remote sensing for detecting carbonaceous water pollution

A reach of the Houston Ship Channel was investigated during three separate overflights correlated with ground truth sampling on the Channel. Samples were analyzed for such conventional parameters as biochemical oxygen demand, chemical oxygen demand, total organic carbon, total inorganic carbon, turbidity, chlorophyll, pH, temperature, dissolved oxygen, and light penetration. Infrared analyses conducted on each sample included reflectance ATR analysis, carbon tetrachloride extraction of organics and subsequent scanning, and KBr evaporate analysis of CCl4 extract concentrate. Imagery which was correlated with field and laboratory data developed from ground truth sampling included that obtained from aerial KA62 hardware, RC-8 metric camera systems, and the RS-14 infrared scanner. The images were subjected to analysis by three film density gradient interpretation units. Data were then analyzed for correlations between imagery interpretation as derived from the three instruments and laboratory infrared signatures and other pertinent field and laboratory analyses.

Davis, E. M.

Estimate of late 1974 stratospheric concentration of gaseous chlorine compounds /ClX/

The total concentration (ClX) versus altitude of Cl-containing molecules (principally HCl, Cl, ClO) is estimated. It is shown that the predicted present stratospheric concentrations are due to photolysis near 30 km of man-made CF2Cl2 and CFCl3, and CCl4 from a ground-level source, either man-made or natural. The contribution of CH3Cl to stratospheric ClX is evaluated from preliminary measurements of the compound at ground level. Although ground-level sources of HCl and Cl2 are large, tropospheric processes preclude significant impact on the stratosphere.

Cicerone, R. J.

Uncertainty propagation in a stratospheric model. I - Development of a concise stratospheric model. II - Monte Carlo analysis of imprecisions due to reaction rates

The paper discusses the development of a concise stratospheric model which uses iteration to obtain coupling between interacting species. The one-dimensional, steady-state, diurnally-averaged model generates diffusion equations with appropriate sources and sinks for species odd oxygen, H2O, H2, CO, N2O, odd nitrogen, CH4, CH3Cl, CCl4, CF2Cl2, CFCl3, and odd chlorine. The model evaluates steady-state perturbations caused by injections of chlorine and NO(x) and may be used to predict ozone depletion. The model is used in a Monte Carlo study of the propagation of reaction-rate imprecisions by calculating an ozone perturbation caused by the addition of chlorine. Since the model is sensitive to only 10 of the more than 50 reaction rates considered, only about 1000 Monte Carlo cases are required to span the space of possible results.

Rundel, R. D.

Temperature dependence of the rate constants for reactions of O/1D/ atoms with a number of halocarbons

Results are reported for an experimental study of the reactions of O(1D) with CCl4, CFCl3, CF2Cl2, CHFCl2, CHF2Cl, and CF2ClCFCl2 over the temperature range from 173 to 343 K, based on the time-resolved emission of O(1D) at 630 nm. The experiments involved photolysis of O3 by Nd-YAG laser pulses and measurements of 630-nm emission intensity in mixtures with He and the various halocarbons. Pseudo-first-order rate constants are derived from plots of the logarithms of the 630-nm emission intensities as a function of time for particular He/O3/halocarbon mixtures, and second-order rate constants are then obtained from plots of these pseudo-first-order rate constants as a function of halocarbon concentration at constant He and O3 concentrations. No temperature dependence of the second-order rate constants is observed over the range studied, within the precision of the measurements. It is found that the rate constants decrease as H is substituted for Cl in a halocarbon molecule and as F is substituted for H or Cl.

Davidson, J. A.

Configurations of base-pair complexes in solutions

A theoretical search for the most stable conformations (i.e., stacked or hydrogen bonded) of the base pairs A-U and G-C in water, CCl4, and CHCl3 solutions is presented. The calculations of free energies indicate a significant role of the solvent in determining the conformations of the base-pair complexes. The application of the continuum method yields preferred conformations in good agreement with experiment. Results of the calculations with this method emphasize the importance of both the electrostatic interactions between the two bases in a complex, and the dipolar interaction of the complex with the entire medium. In calculations with the solvation shell method, the last term, i.e., dipolar interaction of the complex with the entire medium, was added. With this modification the prediction of the solvation shell model agrees both with the continuum model and with experiment, i.e., in water the stacked conformation of the bases is preferred.

Egan, J. T.

The hollow-cathode helium-fluorine laser

It is possible to obtain uniform stable long-pulse excitation (in excess of 100 microsec) in gas mixtures involving highly electronegative constituents (SF6, CCl4, NF3, and I2). Such a system was used to investigate the atomic fluorine laser. In the hollow cathode, lasing on fluorine transitions in the doublet system lasted for up to 80 microsec with no signs of the self-termination as reported previously in positive-column devices. The excitation process of the laser appears to depend heavily upon the fluorine donor utilized. For instance, a single-step process is involved when NF3 is used whereas a two-step process is evident for SF6. The details are discussed.

Crane, J. K.

Natural and anthropogenic trace gases in the southern hemisphere

The complexity of the global environment makes it necessary that many important trace gases in the earth's atmosphere be measured on a global scale before predictions can be made regarding the effects of human activities on the environment. A description is presented of measurements of 14 atmospheric trace gases in the lower atmosphere (0-4 km) of the southern hemisphere. Concentrations are considered of CCl3F, CCl2F2, CHClF2, C2.Cl3.F3, CH3CCl3, CCl4, C2.Cl4, CH3I, CHCl3, CO, CH3Cl, CH4, N2O, and OCS. The obtained data are analyzed and interpreted to statistically quantify the possible differences of concentrations in and above the boundary layer, to model the vertical profile of CH3I, and to use the data in support of previous findings that CH4 is increasing in the atmosphere.

Rasmussen, R. A.

Differences in the concentrations of atmospheric trace gases in and above the tropical boundary layer

Weekly air samples were collected at Cape Kumakahi (0 km) and at nearby Mauna Loa Observatory (3.4 km) which is above the boundary layer. EC/GC and GC/FID techniques were used to measure CH3I, CHCl3, CO and CH4 which are largely natural in origin, and C2Cl4, CCl4, CH3CCl3, (F-11), CCl2F2, (F-12), CHClF, (F-22) and C2F3Cl3 (F-113), which are due to anthropogenic (CCl3F) etc. activities. It was found that all these gases are significantly (alpha is equal to or less than 0.05) more abundant in the boundary layer than above it.

Rasmussen, R. A.

The atmospheric lifetime experiment. I - Introduction, instrumentation, and overview

The Atmospheric Lifetime Experiment is designed to determine accurately the atmospheric concentrations of the four halocarbons CFCl3, CF2Cl2, CCl4, and CH3CCl3, and also of N2O with emphasis on measurement of their long-term trends in the atmosphere. Comparison of these concentrations and trends for the four halocarbons with estimates of their industrial emission rates then enables calculations of their global circulation rates and globally averaged atmospheric lifetimes. The experiment utilizes automated dual-column electron-capture gas chromatographs which sample the background air about 4 times daily at the following globally distributed sites: Adrigole, Ireland, Cape Meares, Oregon; Ragged Point, Barbados; Point Matatula, American Samoa, and Cape Grim, Tasmania. The climatology of these 'clean air' sites and their ability to describe the global air mass are reviewed. The instrumentation and methods for data acquisition and processing are then described. An overview of the data obtained and the trends derived during the 3-year period from July 1978 through June 1981 for each of the five species being measured is presented.

Prinn, R. G.

The Atmospheric Lifetime Experiment. II - Calibration

The calibration standards used in the Atmospheric Lifetime Experiment (ALE) for CFCl3, CF2Cl2, CH3CCl3, and CCl4 are described. This includes the preparation of the primary standards by static dilution and their propagation and stability for the period 1977-1982. Two independent assessments of the absolute concentrations of the primary standards used to initiate the ALE measurements in 1977-1978 are reported. For consistency in the ALE program the values assigned to the primary standards and subsequent working standards used in the field were not altered during the experiment when results of better estimates of the original concentration values were obtained. Rather, the appropriate factors by which the ALE mixing ratios for a given species should be multiplied to obtain the best estimate of the current concentration of a given species, are provided.

Rasmussen, R. A.

The retrieval of atmospheric constituent mixing-ratio profiles from solar absorption spectra

Methods used to determine various atmospheric gas distributions are summarized. The experimentally determined mixing ratio profiles (the mixing ratio of a gas is the ratio of the number of gas molecules to the number of air molecules) of some atmospheric gases are shown. In most in situ experiments stratospheric gas samples are collected at several altitudes by balloon, aircraft, or rocket. These samples are then analyzed by various methods. Mixing ratio profiles of Ci, ClO, and OH were determined by laser induced fluorescence of samples. Others have analyzed gas samples by gas chromatography in order to determine the molecular abundances of CCl2F2, CCl4, CCl3F, CFCl3, CF2Cl2, CHClF2, CH3CCl3, CH4, CO, C2Cl3F3, C2Cl4, C2HCl3, C2H2, C2H4, C2H6, C3H8, C6H6, C7H8, H2, and N2O.

Shaffer, W. A.