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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2014

The Carbon Tetrachloride (CCl4) Budget: Mystery or Not

Carbon tetrachloride (CCl4) is a major anthropogenic ozone-depleting substance and greenhouse gas and has been regulated under the Montreal Protocol. However, atmospheric observations show a very slow decline in CCl4 concentrations, inconsistent with the nearly zero emissions estimate based on the UNEP reported production and feedstock usage in recent years. It is now apparent that there are either unidentified industrial leakages, an unknown production source of CCl4, or large legacy emissions from CCl4 contaminated sites. In this paper we use a global chemistry climate model to assess the budget mystery of atmospheric CCl4. We explore various factors that affect the global trend and the gradient between the Northern and Southern hemispheres or interhemispheric gradient (IHG): emissions, emission hemispheric partitioning, and lifetime variations. We find a present-day emission of 30-50 Gg per yr and a total lifetime 25 - 36 years are necessary to reconcile both the observed CCl4 global trend and IHG.

CC14↗
NASA NTRS2010

UV Absorption Cross Sections of Nitrous Oxide (N2O) and Carbon Tetrachloride (CCl4) Between 210 and 350 K and the Atmospheric Implications

Absorption cross sections of nitrous oxide (N2O) and carbon tetrachloride (CCl4) are reported at five atomic UV lines (184.95, 202.548, 206.200, 213.857, and 228.8 nm) at 27 temperatures in the range 210-350 K. In addition, UV absorption spectra of CCl4 are reported between 200-235 nm as a function of temperature (225-350 K). The results from this work are critically compared with results from earlier studies. For N2O, the present results are in good agreement with the current JPL recommendation enabling a reduction in the estimated uncertainty in the N2O atmospheric photolysis rate. For CCl4, the present cross section results are systematically greater than the current recommendation at the reduced temperatures most relevant to stratospheric photolysis. The new cross sections result in a 5-7% increase in the modeled CCl4 photolysis loss, and a slight decrease in the stratospheric lifetime, from 51 to 50 years, for present day conditions. The corresponding changes in modeled inorganic chlorine and ozone in the stratosphere are quite small. A CCl4 cross section parameterization for use in 37 atmospheric model calculations is presented.

Carlon, Nabilah Rontu↗
NASA NTRS1989

Comparison of experimental and calculated attachment rate constants for CFCl3 and CCl4 in the temperature range 294-500 K

Electron-attachment cross sections and rate constants have been measured and calculated for the dissociative attachment processes e + CFCl3 - Cl(-) + CFCl2 and e + CCl4 - Cl(-) + CCl3. Good agreement over the electron-energy range 1-200 meV is found in energy dependence between present calculated cross sections and experimental cross sections at 300 K. The same calculation, with suitable adjustment of thermal populations, was used to calculate electron-attachment rate constants in the range 50-600 K. Experimental rate constants for CFCl3 and CCl4 were measured at temperatures of 294, 404, and 496 K (CFCl3) and 294, 400, and 500 K (CCl4) using the Cavalleri electron-density sampling method. Good agreement is found between present measurements and calculations, poor agreement with flowing-afterglow Langmuir-probe (FALP) data in CFCl3 at the higher temperatures, and reasonable agreement with FALP data for CCl4.

Orient, O. J.↗
NASA NTRS1986

A global three-dimensional model of the circulation and chemistry of CFCl3, CF2Cl2, CH3CCl3, CCl4, and N2O

The use of a three-dimensional spectral model to study the tropospheric and stratospheric circulation, chemistry, and photochemistry of the CFCl3, CF2Cl2, CH3CCl3, CCl4, and N2O atmospheric species is examined. The components of the model are described. Lifetime, regional, and global trends and budgets for the species are evaluated. Calculated horizontal, vertical, and temporal distributions of the atmospheric species are compared with observations; good correlation is detected. The differences observed between calculated and observed surface distributions of CH3CCl3 and the vertical distribution of CCl4 are analyzed. The calculated global atmospheric lifetimes of CFCl3, CF2Cl2, CCl4, and N2O are 73, 210, 48, and 182 years, respectively.

Golombek, A.↗
NASA NTRS1978

Interhemispheric gradients of CF2Cl2, CFCl3, CCl4, and N2O

Direct real-time gas-chromatographic measurements of CF2Cl2, CFCl3, CCl4, and N2O were made at latitudes from 74 deg N to 62 deg S aboard a NASA Convair 990 as part of the 1976 NASA CV-990 Latitude Survey Mission between Alaska and New Zealand. A difference was found in the average mixing ratios of CF2Cl2 and CFCl3 between the Northern and Southern Hemispheres, but no differences were noted for CCl4 and N2O. The results support some of the previous studies of interhemispheric tropospheric gradients and suggest the lack of any significant tropospheric sinks.

Tyson, B. J.↗
NASA NTRS1985

s-wave threshold in electron attachment - Observations and cross sections in CCl4 and SF6 at ultralow electron energies

The threshold photoionization method was used to study low-energy electron attachment phenomena in and cross sections of CCl4 and SF6 compounds, which have applications in the design of gaseous dielectrics and diffuse discharge opening switches. Measurements were made at electron energies from below threshold to 140 meV at resolutions of 6 and 8 meV. A narrow resolution-limited structure was observed in electron attachment to CCl4 and SF6 at electron energies below 10 meV, which is attributed to the divergence of the attachment cross section in the limit epsilon, l approaches zero. The results are compared with experimental collisional-ionization results, electron-swarm unfolded cross sections, and earlier threshold photoionization data.

Chutjian, A.↗
NASA NTRS1985

Measurements of CCl3F, CCl2F2, CCl4, N2O and SF6 in the Northern Hemisphere stratosphere

An overview of the Department of Energy's High Altitude Sampling Program and some recent trace gas measurement results are presented. Analysis of whole air samples, collected in pressurized bottles, provides information on stratospheric inventories and distributions for CCl3F, CCl2F2, CCl4, N2O and SF6 in the Northern Hemisphere. Based on a linear regression analysis of the data the estimated mean Northern Hemisphere stratospheric concentration of each gas increased as follows: CCl3F changed from 54 to 142 p1/1 (4/74-11/83); CCl2F2 changed from 133 to 268 p1/1 (4/76-11/83); SF6 changed from 160 to 480 f1/1 (4/74-11/83); CC1, changed from 58 to 91 p1/1 (4/75-11/83); N2O changed from 246 to 261 n1/1 (4/76-11/83). The calculated mean Northern Hemisphere stratospheric concentrations of N2O, CCl3F, CCl2F2, and CCl4 after 1980 show larger than expected fluctuations with time. Recent volcanic activity may be a partial cause for these fluctuations through induced changes in stratospheric dynamical processes.

Leifer, R.↗
NASA NTRS1978

Lower stratosphere measurements of variation with latitude of CF2Cl2, CFCl3, CCl4, and N2O profiles in the northern hemisphere

Measurements were made from a U-2 aircraft of profiles of CF2Cl2, CFCl3, CCl4 and N2O in the lower stratosphere in a meridional survey at a longitude of 159 deg W during the period October 1 to November 14, 1976. The latitude distributions obtained show a marked decrease in mixing ratio with increasing latitude from about 7 deg N in the Intertropical Convergence Zone to about 79 deg N. The results suggest the importance of meridional transport and mixing in the stratosphere in accounting, at least in part, for the observed profile variation with latitude. The contaminants C2F4Cl2, C2F3Cl3, CHCCl3 and SF6 were also detected but their mixing ratios were small and no accurate standards were prepared for them.

Vedder, J. F.↗
NASA NTRS1995

The fate of atmospheric phosgene and the stratospheric chlorine loadings of its parent compounds: CCl4, C2Cl4, C2HCL3, CH3CCl3, and CHCl3

A study of the tropospheric and stratospheric cycles of phosgene is carried out to determine its fate and ultimate role in controlling the ozone depletion potentials of its parent compounds. Tropospheric phosgene is produced from the OH-initiated oxidation of C2Cl4, CH3CCl3, CHCl3, and C2HCl3. Simulations using a two-dimensional model indicate that these processes produce about 90 pptv/yr of tropospheric phosgene with an average concentration of about 18 pptv, in reasonable agreement with observations. We estimate a residence time of about 70 days for tropospheric phosgene, with the vast majority being removed by hydrolysis in cloudwater. Only about 0.4% of the phosgene produced in the troposphere avoids wet removal and is transported to the stratosphere, where its chlorine can be released to participate in the catalytic destruction of ozone. Stratospheric phosgene is produced from the photochemical degradation of CCl4, C2Cl4, CHCl3, and CH3CCl3 and is removed by photolysis and downward transport to the troposphere. Model calculations, in good agreement with observations, indicate that these processes produce a peak stratospheric concentration of about 25-30 pptv at an altitude of about 25 km. In contrast to tropospheric phosgene, stratospheric phosgene is found to have a lifetime against photochemical removal of the order of years. As a result, a significant portion of the phosgene that is produced in the stratosphere is ultimately returned to the troposphere, where it is rapidly removed by clouds. This phenomenon effectively decreases the amount of reactive chlorine injected into the stratosphere and available for ozone depletion from phosgene's parent compounds. A similar phenomenon due to the downward transport of stratospheric COFCl produced from CFC-11 is estimated to cause a 7% decrease in the amount of reactive chlorine injected into the stratosphere from this compound. Our results are potentially sensitive to a variety of parameters, most notably the rate of reaction of phosgene with sulfate aerosols. However, on the basis of the observed vertical distribution of COCl2, we estimate that the reaction of COCl2 with sulfate aerosol most likely has a gamma less than 5 x 10(exp -5) and, as a result, has a negligible impact on the stratospheric chlorine loadings of the phosgene parent compounds.

Kindler, T. P.↗
NASA NTRS1990

Application of reversal electron attachment for ultrasensitive detection of thermal electron-attaching molecules - CCl4 and C6H5O2

A standard gas-dilution method was used to determine the selective response of the reversal electron attachment detector to carbon tetrachloride concentrations in nitrogen. Data are provided that determine the lowest concentration of sample detectable with the present instrumental configuration as being below 1.0 part per trillion by volume. The incorporation of a 90-deg electrostatic deflector with the quadrupole mass spectrometer is shown to be vital, and with it, negative-ion quadrupole mass spectrometry is used to characterize the ionization process. Observations are also made of the reversal electron attachment response to nitrobenzene. The analytical potential of reversal electron capture negative-ion mass spectrometry is examined, and areas for future development are discussed.

Bernius, Mark T.↗
NASA NTRS1991

The role of matrix material and CCl4 (electron acceptor) on the ionization mechanisms of matrix-isolated naphthalene

The formation mechanisms and optical properties of polycyclic aromatic hydrocarbons (PAH) isolated in argon and neon matrices were studied in a systematic manner in an attempt to provide spectroscopic data on PAH ions under conditions relevant to astrophysical applications. The results obtained indicate the strong influence of the matrix material on the competing radiative (fluorescence and phosphorescence) and nonradiative (internal conversion and intersystem crossing) relaxation processes of the trapped molecule.

Salama, F.↗
NASA NTRS2016

Model Sensitivity Studies of the Decrease in Atmospheric Carbon Tetrachloride

Carbon tetrachloride (CCl4) is an ozone-depleting substance, which is controlled by the Montreal Protocol and for which the atmospheric abundance is decreasing. However, the current observed rate of this decrease is known to be slower than expected based on reported CCl4 emissions and its estimated overall atmospheric lifetime. Here we use a three-dimensional (3-D) chemical transport model to investigate the impact on its predicted decay of uncertainties in the rates at which CCl4 is removed from the atmosphere by photolysis, by ocean uptake and by degradation in soils. The largest sink is atmospheric photolysis (74% of total), but a reported 10% uncertainty in its combined photolysis cross section and quantum yield has only a modest impact on the modelled rate of CCl4 decay. This is partly due to the limiting effect of the rate of transport of CCl4 from the main tropospheric reservoir to the stratosphere, where photolytic loss occurs. The model suggests large interannual variability in the magnitude of this stratospheric photolysis sink caused by variations in transport. The impact of uncertainty in the minor soil sink (9%of total) is also relatively small. In contrast, the model shows that uncertainty in ocean loss (17%of total) has the largest impact on modelled CCl4 decay due to its sizeable contribution to CCl4 loss and large lifetime uncertainty range (147 to 241 years). With an assumed CCl4 emission rate of 39 Gg year(exp -1), the reference simulation with the best estimate of loss processes still underestimates the observed CCl4 (overestimates the decay) over the past 2 decades but to a smaller extent than previous studies. Changes to the rate of CCl4 loss processes, in line with known uncertainties, could bring the model into agreement with in situ surface and remote-sensing measurements, as could an increase in emissions to around 47 Gg year(exp -1). Further progress in constraining the CCl4 budget is partly limited by systematic biases between observational datasets. For example, surface observations from the National Oceanic and Atmospheric Administration (NOAA) network are larger than from the Advanced Global Atmospheric Gases Experiment (AGAGE) network but have shown a steeper decreasing trend over the past 2 decades. These differences imply a difference in emissions which is significant relative to uncertainties in the magnitudes of the CCl4 sinks.

Carbon Trechloride↗
NASA NTRS2016

SPARC Report on the Mystery of Carbon Tetrachloride

The Montreal Protocol (MP) controls the production and consumption of carbon tetrachloride (CCl4 or CTC) and other ozone-depleting substances (ODSs) for emissive uses. CCl4 is a major ODS, accounting for about 12% of the globally averaged inorganic chlorine and bromine in the stratosphere, compared to 14% for CFC-12 in 2012. In spite of the MP controls, there are large ongoing emissions of CCl4 into the atmosphere. Estimates of emissions from various techniques ought to yield similar numbers. However, the recent WMO/UNEP Scientific Assessment of Ozone Depletion estimated a 2007-2012 CCl4 bottom-up emission of 1-4 Gg/year (1-4 kilotonnes/year), based on country-by-country reports to UNEP, and a global top-down emissions estimate of 57 Gg/ year, based on atmospheric measurements. This 54 Gg/year difference has not been explained. In order to assess the current knowledge on global CCl4 sources and sinks, stakeholders from industrial, governmental, and the scientific communities came together at the “Solving the Mystery of Carbon Tetrachloride” workshop, which was held from 4-6 October 2015 at Empa in Dübendorf, Switzerland. During this workshop, several new findings were brought forward by the participants on CCl4 emissions and related science.

Ahmadzai, Husamuddin↗
NASA NTRS1983

A two-dimensional photochemical model of the atmosphere. I Chlorocarbon emissions and their effect on stratospheric ozone

A two-dimensional photochemical model is used to examine changes to the ozone layer caused by emissions of CFCl3, CF2Cl2, CH3CCl3 and CCl4. The influence of a possible secular increase in tropospheric methane up to 2 percent per year was found to be small, although it acts to mask decreases in total ozone caused by the chlorocarbons. Increasing NO(x) emissions caused by industralization also tend to mask decreases in total ozone and may have caused total ozone to increase by about 1 percent. The model-calculated ozone decreases are estimated to be about 3 percent by 1980. This estimate is higher than estimates by similar models, although it is noted that CCl4 and CH3CCl3 emissions are included in the model in addition to CFCl3 and CF2Cl2. This is significant because the model indicates that CCl4 has dominated the ozone depletions so far, and knowledge of the historical emission rate of CCl4 to the atmosphere is incomplete. There remain sufficient significant disagreements between theoretical and observed concentrations and variabilities, particularly for odd nitrogen and ClO, to caution against assigning too much confidence in the calculated ozone depletion.

Gidel, L. T.↗
NASA NTRS1977

Photodecomposition of chloromethanes adsorbed on silica surfaces

Irradiation of CCl4, CFCl3, and CF2Cl2 in the presence of C2H6 in vessels containing silica sand or fused quartz tubing results in the formation of chlorine-containing products. The formation of these compounds occurs at wavelengths extending up to approximately 400 nm, that is, at wavelengths well beyond the absorption threshold of the chloromethanes in the gas phase. It is suggested that CCl4 adsorbed on silica surfaces photodissociates to yield CCl3 and CCl2 species. The poor material balance obtained in these experiments indicates that several of the chlorine-containing fragments are strongly adsorbed on the surface. At a CCl4 pressure of 13 Pa (0.1 torr), photolysis with 366 nm light in the presence of sand results in the decomposition of one molecule for every 10,000 photons striking the surface. Under otherwise identical conditions, the photon-induced breadkdown of CFCl3 and CF2Cl2 is respectively only 10% or 3% as efficient.

Ausloos, P.↗
NASA NTRS1975

A search for chemical laser action in low pressure metal vapor flames

Optical emissions were studied from low pressure (approximately 1 torr) dilute diffusion flames of Ca and Mg vapor with O2, N2O and mixtures of CCl4 and O2. The Ca flames with O2 and N2O revealed high vibrational excitation of the product CaO molecule (up to v=30). The flames with CCl4 revealed extreme nonequilibrium metal atom electronic excitation, up to the metal atom ionization limit (6.1 eV for Ca, 7.6 eV for Mg). The metal atom excited electronic state populations did not follow a Boltzmann distribution, but the excitation rates ('pumping rate') were found to obey an Arrhenius-type expression, with the electronic excitation energy playing the role of activation energy and a temperature of about 5000 K for triplet excited states and 2500 K for singlets (vs. approximately 500 K translational temperature).

Zwillenberg, M. L.↗
NASA NTRS1982

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.↗
NASA NTRS1985

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.↗