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At least 19 records

Greenhouse effect of chlorofluorocarbons and other trace gases

A comparison is made of the radiative (greenhouse) forcing of the climate system due to changes of atmospheric chlorofluorocarbons and other trace gases. It is found that CFCs, defined to include chlorofluorocarbons, chlorocarbons, and fluorocarbons, now provide about one-quater of current annual increases in anthropogenic greenhouse climate forcing. If the growth rates of CFC production in the early 1970s had continued to the present, current annual growth of climate forcing due to CFCs would exceed that due to CO2.

Hansen, James↗

Robust perfluorinated porous organic networks: Succinct synthetic strategy and application in chlorofluorocarbons adsorption

Fluorinated porous organic networks (F-PONs) have demonstrated unique properties and applications, but approaches capable of affording F-PONs with high fluorine content and robust nanoporous architecture under metal-free and easy handling conditions are still rarely reported. Herein, using polydivinylbenzene (PDVB) as an easily available precursor, a novel and straightforward approach was developed to afford F-PONs via a dehydrative Friedel-Crafts reaction using perfluorinated benzylic alcohols as the cross-linking agent promoted by Brønsted acid (trifluoromethanesulfonic acid. Furthermore, the afforded material (F-PDVB) featured high fluorine content (22 at.%), large surface area (771 m 2 ∙g -1 ), and good chemical/thermal stability, rendering them as promising candidates for the adsorption of CO 2 , hydrocarbons, fluorocarbons, and chlorofluorocarbons, with weight capacities up to 520 wt% being achieved. This simple methodology can be extended to fabricate fluorinated hyper-crosslinked polymers (F-HCPs) from rigid aromatic monomers. The progress made in this work will open new opportunities to further expand the involvement of fluorinated materials in large scale applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Greenhouse effect due to chlorofluorocarbons - Climatic implications

The infrared bands of chlorofluorocarbons and chlorocarbons enhance the atmospheric greenhouse effect. This enhancement may lead to an appreciable increase in the global surface temperature if the atmospheric concentrations of these compounds reach values of the order of 2 parts per billion.

Ramanathan, V.↗

Atmospheric degradation mechanisms of hydrogen containing chlorofluorocarbons (HCFC) and fluorocarbons (HFC)

The current knowledge of atmospheric degradation of hydrogen containing chlorofluorocarbons (HCFC 22 (CHClF2), HCFC 123 (CHCl2CF3), HCFC 124 (CHClFCF3), HCFC 141b (CFCl2CH3), HCFC 142b (CF2ClCH3)) and fluorocarbons (HFC 125 (CHF2CF3), HFC 134a (CH2FCF3), HFC 152a (CHF2CH3)) is assessed. Except for the initiation reaction by OH radicals, there are virtually no experimental data available concerning the subsequent oxidative breakdown of these molecules. However, from an analogy to the degradation mechanisms of simple alkanes, some useful guidelines as to the expected intermediates and final products can be derived. A noteable exception from this analogy, however, appears for the oxi-radicals. Here, halogen substitution induces new reaction types (C-Cl and C-C bond ruptures) which are unknown to the unsubstituted analogues and which modify the nature of the expected carbonyl products. Based on an evaluation of these processes using estimated bond strength data, the following simplified rules with regards to the chlorine content of the HCFC's may be deduced: (1) HCFC's containing one chlorine atom such as 22 and 142b seem to release their chlorine content essentially instantaneous with the initial attack on the parent by OH radicals, and for HCFC 124, such release is apparently prevented; (2) HCFC's such as 123 and 141b with two chlorine atoms are expected to release only one of these instantaneously; and the second chlorine atom may be stored in potentially long-lived carbonyl compounds such as CF3CClO or CClFO.

Zellner, Reinhard↗

What Would Have Happened to the Ozone Layer if Chlorofluorocarbons (CFCs) had not been Regulated?

Ozone depletion by chlorofluorocarbons (CFCs) was first proposed by Molina and Rowland in their 1974 Nature paper. Since that time, the sci entific connection between ozone losses and CFCs and other ozone depl eting substances (ODSs) has been firmly established with laboratory m easurements, atmospheric observations, and modeling research. This science research led to the implementation of international agreements t hat largely stopped the production of ODSs. In this study we use a fu lly-coupled radiation-chemical-dynamical model to simulate a future world where ODSs were never regulated and ODS production grew at an ann ual rate of 3%. In this "world avoided" simulation 1.7 % of the globa lly-average column ozone is destroyed by 2020, and 67% is destroyed b y 2065 in comparison to 1980. Large ozone depletions in the polar region become year-round rather than just seasonal as is currently observ ed in the Antarctic ozone hole. Very large temperature decreases are observed in response to circulation changes and decreased shortwave radiation absorption by ozone. Ozone levels in the tropical lower strat osphere remain constant until about 2053 and then collapse to near ze ro by 2058 as a result of heterogeneous chemical processes (as curren tly observed in the Antarctic ozone hole). The tropical cooling that triggers the ozone collapse is caused by an increase of the tropical upwelling. In response to ozone changes, ultraviolet radiation increa ses, more than doubling the erythemal radiation in the northern summer midlatitudes by 2060.

Newman, Paul A.↗

Molecular‐Level Insight into the Chlorofluorocarbons Adsorption by Defective Covalent Organic Polymers

Abstract Halocarbons have important industrial applications, but because of their contribution to global warming and the fact that they can cause ozone depletion, they are considered highly toxic. Hence, the techniques that can capture and recover the used halocarbons with energy‐efficient methods have been recently received greater attention. In this contribution, we report the capture of dichlorodifluoromethane (R12), which has high global warming and ozone depletion potential, using covalent organic polymers (COPs). The defect‐engineered COPs were synthesized and demonstrated outstanding sorption capacities, ~226 wt % of R12 combined with linear‐shaped adsorption isotherms. We further identified the plausible microscopic adsorption mechanism of the investigated COPs via grand canonical Monte Carlo simulations applied to non‐defective and a collection of atomistic models of the defective COPs. The modeling work suggests that significant R12 adsorption performance is attributed to a gradual increment of porosities due to isolated/interconnected micro‐/meso‐pore channels and the change of the long‐range ordering of both COPs. The successive hierarchical‐pore‐filling mechanism promotes R12 molecular adsorption via moderate van der Waals adsorbate‐adsorbent interactions in the micropores of both COPs at low pressure followed by adsorbate‐adsorbate interactions in the extra‐voids created at moderate to high pressure ranges. This continuous pore‐filling mechanism makes defective COPs as promising sorbents for halocarbon adsorption.

Shen, Jian↗

Physical properties of alternatives to the fully halogenated chlorofluorocarbons

Presented here are recommended values and correlations of selected physical properties of several alternatives to the fully halogenated chlorocarbons. The quality of the data used in this compilation varies widely, ranging from well-documented, high accuracy measurements from published sources to completely undocumented values listed on anonymous data sheets. That some of the properties for some fluids are available only from the latter type of source is clearly not the desired state of affairs. While some would reject all such data, the compilation given here is presented in the spirit of laying out the present state of knowledge and making available a set of data in a timely manner, even though its quality is sometimes uncertain. The correlations presented here are certain to change quickly as additional information becomes available.

Mclinden, Mark O.↗

Bayesian Assessment of Chlorofluorocarbon (CFC), Hydrochlorofluorocarbon (HCFC) and Halon Banks Suggest Large Reservoirs Still Present in Old Equipment

Halocarbons contained in equipment such as air conditioners, fire extinguishers, and foams continue to be emitted after production has ceased. These ‘banks’ within equipment and applications are thus potential sources of future emissions, and must be carefully accounted for in order to evaluate nascent production versus banked emissions. Here, we build on a probabilistic Bayesian model, previously developed to quantify CFC-11, 12 and 113 banks and their emissions. We extend this model to a suite of the major banked chemicals regulated under the Montreal Protocol (HCFC-22, HCFC-141b, and HCFC-142b, halon-1211, and halon-1301, and CFC-114 and CFC-115) along with CFC-11, 12 and 113 in order to quantify a fuller range of ozone-depleting substance banks by chemical and equipment type. We show that if atmospheric lifetime and prior assumptions are accurate, banks are very likely larger than previous international assessments suggest, and that total production has been very likely higher than reported. We identify that banks of greatest climate-relevance, as determined by global warming potential weighting, are largely concentrated in CFC-11 foams and CFC-12 and HCFC-22 non-hermetic refrigeration. Halons, CFC-11, and 12 banks dominate the banks weighted by ozone depletion potential. Thus, we identify and quantify the uncertainties in substantial banks whose future emissions will contribute to future global warming and delay ozone hole recovery if left unrecovered.

Halocarbons↗

Advanced Global Atmospheric Gases Experiment (AGAGE): MIT Contribution

We describe in detail the instrumentation and calibrations used in the ALE, GAGE and AGAGE experiments and present a history of the majority of the anthropogenic ozone- depleting and climate-forcing gases in air based on these experiments. Beginning in 1978, these three successive automated high frequency in-situ experiments have documented the long-term behavior of the measured concentrations of these gases over the past twenty years, and show both the evolution of latitudinal gradients and the high frequency variability due to sources and circulation. We provide estimates of the long-term trends in total chlorine contained in long- lived halocarbons involved in ozone depletion. We summarize interpretations of these measurements using inverse methods to determine trace gas lifetimes and emissions. Finally, we provide a combined observational and modeled reconstruction of the evolution of chlorocarbons by latitude in the atmosphere over the past sixty years which can be used as boundary conditions for interpreting trapped air in glaciers and oceanic measurements of chlorocarbon tracers of the deep oceanic circulation. Some specific conclusions are: (a) International compliance with the Montreal Protocol is so far resulting in chlorofluorocarbon and chlorocarbon mole fractions comparable to target levels, (b) Mole fractions of total chlorine contained in long-lived halocarbons (CCl2F2, CCl3F, CH3CCl3, CCl4, CHClF2, CCl2FCClF2, CH3Cl, CH2Cl2, CHCl3, CCl2=CCl2) in the lower troposphere reached maximum values of about 3.6 ppb in 1993 and are beginning to slowly decrease in the global lower atmosphere, (c) The chlorofluorocarbons have atmospheric lifetimes consistent with destruction in the stratosphere being their principal removal mechanism, (d) Multi-annual variations in chlorofluorocarbon and chlorocarbon emissions deduced from ALUGAGWAGAGE data are consistent approximately with variations estimated independently from industrial production and sales data where available (CCl2F2 (CFC-12) and CCl2FCClF2 (CFC-113) show the greatest discrepancies), (e) The mole fractions of the hydrochlorofluorocarbons and hydrofluorocarbons, which are replacing the regulated halocarbons, are rising very rapidly in the atmosphere but, with the exception of the much longer manufactured CHClF2 (HCFC-22), they are not yet at levels sufficient to contribute significantly to atmospheric chlorine loading. These replacement species could in the future provide independent estimates of the global weighted-average OH concentration provided their industrial emissions are accurately documented, (f) In the future, analysis of pollution events measured using high frequency in-situ measurements of chlorofluorocarbons and their replacements may enable emission estimates at the regional level which, together with industrial end-use data, are of sufficient accuracy to be capable of identifying regional non-compliance with the Montreal Protocol.

Kurylo, Michael↗

Transport processes and ozone perturbations

Current understanding of stratospheric transport in the meridional plane is reviewed, and the implications of that conceptual framework for the ozone response to chlorofluorocarbon increases are considered. The possibility of seasonal and latitudinal variations in that response is stressed. Calculations of the changes in ozone that may have occurred between the period before widespread chlorofluorocarbon usage and the present day, and the changes that would be expected to occur at steady state for 1980 chlorofluorocarbon production levels, are presented. Finally, some of the uncertainties in the adopted transport framework and its applicability to the evaluation of future perturbations are explored.

Solomon, S.↗

HFE 7100 Compatibility with Orbiter Materials

Chlorofluorocarbon (CFC) 113 is currently specified as the precision cleaning and verification fluid for orbiter materials. The production ban of CFC 113, an ozone-depleting chlorofluorocarbon, has resulted in a search for a replacement cleaning fluid. Recently, the 3M Company announced the manufacture of a new class of cleaning fluids, hydrofluoroethers. The first in this class of cleaning fluids is HFE 7100, perfluorobutyl methyl ether. This cleaning fluid has been submitted for consideration as a replacement for CFC 113. One of the requirements of the certification process for a replacement cleaning fluid is compatibility testing. The Johnson Space Center (JSC) Materials and Manufacturing Division has requested that NASA JSC White Sands Test Facility perform the compatibility testing with HFE 7100 on selected orbiter materials. Most of the materials selected for testing were previously evaluated for compatibility with CFC 113. Some of the materials are new additions to the orbiter or were not available when the compatibility testing was performed with CFC 113. These materials were evaluated with both cleaning fluids and the results were used to compare the response to the cleaning fluid and to satisfy the certification process requirements. It was found that HFE 7100 is generally compatible with the materials tested.

Chlorofluorocarbon↗

Chlorofluoromethanes in the stratosphere and some possible consequences for ozone

Inert chlorofluoromethanes are used by man as refrigerants and aerosol propellants. These substances eventually escape and diffuse upward into the stratosphere. At great enough heights, UV sunlight can photodissociate these chlorofluorocarbons into chlorine atoms which will catalytically destroy ozone molecules. Chlorofluoromethane production has been increasing steadily in recent years to its present level of about a megaton per year, and chlorofluorocarbon usage will probably continue to grow in the future. Calculations with a one-dimensional time-dependent atmospheric model suggests that, if projected increases in chlorofluoromethane use materialize and there is no tropospheric destruction mechanism for these gases, the total global abundance of ozone may be reduced by more than 20 per cent over the next 50 years. If the residence times for these fluorocarbons in the troposphere are in the range of 10-30 years, however, predicted ozone depletions would be significantly smaller.

Turco, R. P.↗

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.↗

Global three-dimensional model calculations of the budgets and present-day atmospheric lifetimes of CF2ClCFCl2 (CFC-113) and CHClF2 (CFC-22)

The annual percentage increases in concentrations of the chlorofluorocarbons CFC-113 (an industrial solvent) and CFC-22 (a refrigerant) are the highest among major chlorofluorocarbons in the atmosphere today. The present-day atmospheric lifetimes for these species are computed using a global three-dimensional dynamical-chemical model. The present-day lifetimes of both are long (15.5 years for CFC-22 and 136 or 195 years for CFC-113, depending on assumed O2 absorption cross sections), underscoring the need to decrease their emissions in order to minimize their future role in ozone destruction and greenhouse warming.

Golombek, Amram↗

Natural and anthropogenic perturbations of the stratospheric ozone layer

The paper reviews potential causes for reduction in the ozone abundance. The response of stratospheric ozone to solar activity is discussed. Ozone changes are simulated in relation with the potential development of a fleet of high-speed stratospheric aircraft and the release in the atmosphere of chlorofluorocarbons. The calculations are performed by a two-dimensional chemical-radiative-dynamical model. The importance of heterogeneous chemistry in polar stratospheric clouds and in the Junge layer (sulfate aerosol) is emphasized. The recently reported ozone trend over the last decade is shown to have been largely caused by the simultaneous effects of increasing concentrations of chlorofluorocarbons and heterogeneous chemistry. The possibility for a reduction in stratospheric ozone following a large volcanic eruption such as that of Mount Pinatubo in 1991 is discussed.

Brasseur, Guy P.↗

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.↗

Biogenic and anthropogenic trace gases in the atmosphere

This paper illustrates the importance of biogenic and anthropogenic trace gases for the global environment and for the climate system. The paper briefly reviews the currently available estimates of sources and strengths of the biogenic and anthropogenic gases on the global scale. One of the major concerns for the global environment is the rapid increase in the concentration of long-lived trace gases such as CO2, CH4, N2O and the chlorofluorocarbons. The trend in the carbon dioxide concentration, as a result of fossil-fuel burning, is of the order of 0.4 percent per year, and this trend is related to the CO2 uptake by the ocean and by terrestrial ecosystems, which are likely to be modified if the planet warms up in the forthcoming decades. The concentrations of methane and nitrous oxide are increasing by 0.9 and 0.25 percent per year, respectively. In the case of the most widely used chlorofluorocarbons, trends as large as 10 percent per year or more are being measured.

Brasseur, G. P.↗