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At least 19 records

Global trends and annual releases of CCl3F and CCl2F2 estimated from ALE/GAGE and other measurements from July 1978 to June 1991

Thirteen years of Atmospheric Lifetime Experiment/Global Atmospheric Gases Experiment CCl3F and CCl2F2 measurements at five remote, surface, globally distributed sites are analyzed. Comparisons are made against shipboard measurements by the Scripps Institution of Oceanography (SIO) group and archived air samples collected at Cape Grim, Tasmania, since 1978. CCl3F in the lower troposphere was increasing at an average rate of 9.2 ppt/yr over the period July 1978 to June 1988. CCl2F2 was increasing at an average 17.3 ppt/yr in the lower troposphere over the same period. However, between July 1988 and June 1991 the increases of CCl3F and CCl2F2 in this region have averaged just 7.0 ppt/yr and 15.7 ppt/yr, respectively. The rate of increase has been decreasing 2.4 ppt/yr(exp 2) and 2.9 ppt/yr(exp 2) over this 3-year period. Based on a recent scenario of the global releases of these compounds and using the new calibration scale SIO 1993, the equilibrium lifetimes are estimated to be 44 +17/-10 and 180 +820/-81 years for CCl3F and CCl2F2, respectively. Using these lifetime estimates and a two-dimensional model, it is estimated that global releases of these two chlorofluorocarbons in 1990 were 249 +/- 28 x 10(exp 6) kg for CCl3F and 366 +/- 30 x 10(exp 6) kg for CCl2F2. It is also estimated that combined releases of these chlorofluorocarbons in 1990 were 21 +/- 5% less than those in 1986.

Cunnold, D. M.↗

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.↗

The Seasonal and Interannual Variability of the Budgets of N2O and CCl3F

The 6-year wind archives from the Goddard Institute for Space Studies/Global Climate-Middle Atmosphere Model (GISS/GCMAM) were in- put to the GISS/Harvard/Irvine Chemical Transport Model (G/H/I CTM) to study the seasonal and interannual variability of the budgets and distributions of nitrous oxide (N2O) and trichlorofluoromethane (CCl3F), with the corresponding chemical loss frequencies recycled and boundary conditions kept unchanged from year to year. The effects of ozone feedback and quasi-biennial oscillation (QBO) were not included. However, the role of circulation variation in driving the lifetime variability is investigated. It was found that the global loss rates of these tracers are related to the extratropical planetary wave activity, which drives the tropical upward mass flux. For N2O, a semiannual signal in the loss rate variation is associated with the interhemispheric asymmetry in the upper stratospheric wave activity. For CCl3F, the semiannual signal is weaker, associated with the comparatively uniform wave episodes in the lower stratosphere. The loss rates lag behind the wave activity by about 1-2 months. The interannual variation of the GCM generated winds drives the interannual variation of the annually averaged lifetime. The year-to-year variations of the annually averaged lifetimes can be about 3% for N2O and 4% for CCl3F.

Wong, Sun↗

Materials Data on CCl3F by Materials Project

CCl3F is Iron carbide-derived structured and crystallizes in the orthorhombic Pbca space group. The structure is zero-dimensional and consists of eight trichlorofluoromethane molecules. C4+ is bonded in a tetrahedral geometry to three Cl1- and one F1- atom. All C–Cl bond lengths are 1.77 Å. The C–F bond length is 1.37 Å. There are three inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a single-bond geometry to one C4+ atom. In the second Cl1- site, Cl1- is bonded in a single-bond geometry to one C4+ atom. In the third Cl1- site, Cl1- is bonded in a single-bond geometry to one C4+ atom. F1- is bonded in a single-bond geometry to one C4+ atom.

36 MATERIALS SCIENCE↗

Methane concentrations and source strengths in urban locations

The results of a six year measurement of trace gases in 18 different urban and remote areas throughout the Northern and Southern Hemispheres are reported. It is found that the measurements are consistent with a yearly atmospheric release of 30 to 60 megatons of CH4 in urban environments. Concentrations of CCl3F, CCl2F2, and CH3CCl3 were also found to be higher in the same urban samples than in corresponding samples from remote areas. The 'urban excess' (urban concentration minus remote concentration) was generally 1000 to 2000 times larger on a molar basis for CH4 than for CCl3F. The fraction of world-wide methane release occurring in the urban environment is estimated from the concentration ratios for CH4 vs CCl3F. It is shown that about 8 to 15 percent of atmospheric methane release occurs in urban areas.

Blake, D. R.↗

Atmospheric concentrations and behavior of halocarbons and methane

The atmospheric concentrations of halocarbons and methane in the troposphere and stratosphere were precisely measured by grab-sampling followed by gas-chromatographic analysis in the laboratory. Chlorofluorocarbons such as CCl2F2 and CCl3F have received a great deal of attention due to their probable impact on the stratospheric ozone: the chlorofluorocarbons accumulated in the troposphere are eventually decomposed by photolysis in the stratosphere releasing Cl radicals which in turn participate in the ClO sub x-catalytic chain destroying the ozone, especially in the upper stratosphere. Methane reacts with Cl in the stratosphere reducing the ozone depletion, while its source and future trend of concentration in the troposphere are uncertain. The study of their distribution and behavior in the atmosphere are therefore very important. After the extensive survey of the locations for collection of atmospheriic samples representing the midlatitudes Northern Hemisphere (N.H.) without local contamination, we have measured the concentrations of CCl2F2, CCl3F, CH3CCl3, CC1, CHCl=CCl2 and CCl2=CCl2 with plus or minus 1 pptv precision in samples collected in Hokkaido and west coast Tohoku area (the northern part of Japan, 40 deg to 45 deg N) every summer and winter since 1979. The observed concentrations of CCl2F2 and CCl3F are now above 360 and 200 pptv, respectively, and have been steadily increasing by approx. 15 and approx. 8 pptv/year during the last several years.

Makide, Y.↗

Investigation of an inverted meniscus heat pipe wick concept

A wicking concept is described for efficient evaporation of heat pipe working fluids under diverse conditions. It embodies the high heat transfer coefficient of the circumferential groove while retaining the circumferential fluid transport capability of a thick porous wick or screen. Experimental tests are described which substantiate the efficacy of the evaporation technique for a circumferentially-grooved heat pipe charged alternately with ammonia and R-ll (CCl3F). With ammonia, heat transfer coefficients in the range of 2 to 2.7 W/sq cm K were measured at heat flux densities up to 20 W/sq cm while, with R-ll, a heat transfer coefficient of l.0 W/sq cm K was measured with flux densities up to 5 W/sq cm. Heat transfer coefficients and flux densities were unusually high compared to literature data for other nonboiling evaporative surfaces.

Saaski, E. W.↗

Thermodynamic properties of gaseous fluorocarbons and isentropic equilibrium expansions of two binary mixtures of fluorocarbons and argon

Equations and computer code are given for the thermodynamic properties of gaseous fluorocarbons in chemical equilibrium. In addition, isentropic equilibrium expansions of two binary mixtures of fluorocarbons and argon are included. The computer code calculates the equilibrium thermodynamic properties and, in some cases, the transport properties for the following fluorocarbons: CCl2F, CCl2F2, CBrF3, CF4, CHCl2F, CHF3, CCL2F-CCl2F, CCLF2-CClF2, CF3-CF3, and C4F8. Equilibrium thermodynamic properties are tabulated for six of the fluorocarbons(CCl3F, CCL2F2, CBrF3, CF4, CF3-CF3, and C4F8) and pressure-enthalpy diagrams are presented for CBrF3.

Talcott, N. A., Jr.↗

The reactions of CCl2FO2 with NO and NO2 and the thermal decomposition of CCl2FO2NO2

CCl2FO2 radicals are produced in the stratosphere from the oxidation of CCl2F radicals produced from the photodissociation of CCl3F. The reactions of CCl2FO2 with NO and NO2 were studied by steady state photolysis at 1 atm and 286-305 K. The reactions were CCl2FO2 + NO yields CCl2FO + NO2 and CCl2FO2 + NO2 (+M) yields CCl2FO2NO2 (+M) with k3/k4 = 0.58 plus or minus 0.10 over this temperature range.

Simonaitis, R.↗

Interlaboratory comparison of fluorocarbons-11, -12, methylchloroform and nitrous oxide measurements

Measurements conducted by 19 participating laboratories were considered in the reported interlaboratory comparison study. The results show that there is considerable disagreement among laboratories regarding the absolute concentrations of all four trace gases (CCl3F, CCl2F2, H3CCl3, N2O). The magnitude of this disagreement is discussed. Laboratories in Group II showed considerable disagreement among themselves. Their results were scattered within large intervals of concentration. Laboratories in Group I (using common standards) were in excellent (+ or - 5%) agreement among themselves. A systematic disagreement was noted between Groups I and II laboratories. Generally, the mean values of concentrations determined from the measurements of Group II laboratories were lower than the mean values reported by Group I laboratories.

Rasmussen, R. A.↗

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 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.↗

Halocarbon concentration patterns associated with frontal passages

The atmospheric mixing ratios of CCl2F2 (F-12) and CCl3F (F-11) increase abruptly up to 14 ppt (F-12) and 8 ppt (F-11) after strong cold fronts pass and decrease abruptly after warm fronts pass at a semicontinuous monitoring station near Pullman, WA (46 deg 42 min N, 117 deg 10 min W). It is concluded that air masses from higher latitudes (above 60 deg N) can have F-12 and/or F-11 concentrations as much as 5 percent higher than mid-latitude air masses. Conversely, nitrous oxide shows no significant changes during frontal passages and is uniformly distributed between air masses.

Carter, M. W.↗

Atmospheric trace gases - Trends and distributions over the last decade

Concentrations of the halocarbons CCl3F (F-11), CCl2F2 (F-12), CCl4, and CH3CCl3, methane (CH4), and nitrous oxide (N2O) over the decade between 1975 and 1985 are reported, based on measurements taken every January at the South Pole and in the Pacific Northwest. The concentrations of F-11, F-12, and CH3CCl3 in both hemispheres are now more than twice their concentrations 10 years ago. However, the annual rates of increase of F-11, F-12, and CH3CCl3 are now considerably slower than earlier in the decade, reflecting in part the effects of a ban on their nonessential uses. Continued increases in these trace gas concentrations may warm the earth and deplete the stratospheric ozone layer, which may cause widespread climatic changes and affect global habitability.

Rasmussen, R. A.↗

Balloon-borne cryogenic spectrometer for measurement of lower stratospheric trace constituents

A liquid-nitrogen cooled, multidetector Fourier transform spectrometer has been constructed to measure minor stratospheric constituents via high resolution, earth-limb emission spectroscopy from a balloon-borne platform. Cryogenic cooling, combined with the use of extrinsic silicon photoconductor detectors cooled to liquid-helium temperature, allows the detection of weak emission features of gaseous species. The spectrometer has two basic scan modes: the first mode records the continuous spectrum from 650-2100/cm with 0.2/cm resolution; the second simultaneously records four preselected narrow intervals (about 175/cm bandpass each) with 0.02/cm resolution, unapodized. Filtering of the interferogram signal is done by real-time, digital signal processing. The most important feature of this flat mirror Michelson system, with respect to remote balloon-borne operation, is the dynamic alignment system which maintains the relative parallelism of the two flat reflectors of the interferometer. Species identified to date in data obtained during a Nov. 6, 1984, flight include: CO2, O3, H2O, CH4, HNO3, N2O, NO2, NO, CCl3F (Freon-11) and CF2Cl2 (Freon-12).

Brasunas, J. C.↗

Proposed reference models for CO2 and halogenated hydrocarbons

The vertical distribution of carbon dioxide, halocarbons and their sink products, HCl and HF, have become available, mainly by means of balloon measurements. Most measurements were made at northern mid-latutudes, but some constituents were measured at tropical latitudes and in the Southern Hemisphere as well. An attempt is made here to combine the available data for presentation of reference models for CO2, CCl4 CCl3F, CCl2F2, CClF3, CF4, CCl2F-CClF2, CClF2-CClF2, CClF2-CF3, CF3-CF3, CH3Cl, CHClF2, CH3-CCl3, CBrClF2, CBrF3, HCl and HF.

Fabian, P.↗

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.↗