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1.
The absorption cross-sections of HCFC-123 (CF3–CHCl2), HCFC-141b (CH3–CFCl2) and HCFC-142b (CH3–CF2Cl) are measured between 170 and 250 nm for temperatures ranging from 295 to 210 K with uncertainties between 2 and 4%. They are compared with other available determinations. Temperature effects are discussed and parametrical formulae are proposed to compute the absorption cross-section for wavelengths and temperatures useful in atmospheric modelling calculations. Photodissociation coefficients are presented and their temperature-dependence is discussed.  相似文献   

2.
Ultraviolet absorption cross-sections of trifluoro-bromo-methane (CF3Br-Halon 1301), difluoro-dibromo-methane (CF2Br2-Halon 1202) and of difluoro-bromo-chloro-methane (CF2BrCl-Halon 1211) are measured in the wavelength interval 172–304 nm for temperatures ranging from 210 to 295 K with uncertainties of between 2 and 4%. They are compared with previous measurements available at room temperature. Temperature effects are discussed and parametrical formulae are proposed to compute the absorption cross-sections for wavelengths and temperatures useful in atmospheric modelling calculations. Photodissociation coefficients are presented and their temperature dependence is discussed.  相似文献   

3.
The temperature-dependent ultraviolet absorption cross-sections of CF3-CHFCI (HCFC-124) have been measured between 170 and 230 nm for temperatures ranging from 295 to 210 K, with uncertainties between 2 and 4%. These results are compared with other available sets of determinations. Temperature effects are discussed and the photodissociation coefficients, presented with their temperature dependence, are calculated. Implication of the temperature dependences on the stratospheric chemistry is also discussed. Parametrical formulae are proposed to compute absorption crosssection values for wavelengths and temperatures useful in modelling calculations.  相似文献   

4.
Oxidation reactions of the proposed CFC substitutes HCFC-123 (CF3CHCl2) and HCFC-141b (CFCl2CH3) have been studied in the laboratory using long-path Fourier transform infrared spectroscopy. The air oxidation of the HCFCs was initiated by the photolysis of Cl2 forming Cl atoms that abstract H atoms from the HCFC. CF3C(O)Cl was the only carbon containing compound observed in the infrared spectrum of the products of the HCFC-123/Cl2 irradiations and its yield was approximately one. The product data are consistent with formation of CF3C(O)Cl by Cl elimination of the intermediate halogenated alkoxy radical CF3CCl2O. The Cl-initiated oxidation of HCFC-141b led to the formation of CO and C(O)FCl. The product data are consistent with a 1 : 1 relationship between C(O)FCl formed and HCFC-141b reacted. Product data were compatible with both decomposition by cleavage of the C–C bond of the radical CFCl2CH2O leading to the prompt generation of C(O)FCl and reaction of the radical with O2 forming the two carbon halogenated aldehyde CFCl2CH(O), which in the presence of Cl was likely oxidized to C(O)FCl. An approximate method was developed in which the ratio was extracted from analysis of the time evolution of HCFC-141b, C(O)FCl, and CO. The data suggest that the contributions are comparable.  相似文献   

5.
The ultraviolet absorption cross sections were measured for CF3Br, CF2ClBr, CF2Br-CF2Br, CF2Br2, CHF2Br, CHFBr-CF3, CH2Br-CF3, CHClBr-CF3 in the wavelength range 190–320 nm at 295 K. The photolysis is concluded to be the minor atmospheric sink for CHF2Br, CHFBr-CF3, CH2Br-CF3, CHClBr-CF3.  相似文献   

6.
The set of high-resolution infrared solar observations made with the Atmospheric Trace Molecule Spectroscopy (ATMOS)-Fourier transform spectrometer from onboard Spacelab 3 (30 April-1 May 1985) has been used to evaluate the total budgets of the odd chlorine and fluorine chemical families in the stratosphere. These budgets are based on volume mixing ratio profiles measured for HCl, HF, CH3Cl, ClONO2, CCl4, CCl2F2, CCl3F, CHClF2, CF4, COF2, and SF6 near 30° north latitude. When including realistic concentrations for species not measured by ATMOS, i.e., the source gases CH3CCl3 and C2F3Cl3 below 25 km, and the reservoirs ClO, HOCl and COFCl between 15 and 40 km (five gases actually measured by other techniques), the 30° N zonal 1985 mean total mixing ratio of chlorine, Cl, was found to be equal to (2.58±0.10) ppbv (parts per billion by volume) throughout the stratosphere, with no significant decrease near the stratopause. The results for total fluorine indicate a slight, but steady, decrease of its volume mixing ratio with increasing altitude, around a mean stratospheric value of (1.15±0.12) ppbv. Both uncertainties correspond to one standard deviation. These mean springtime 1985 stratospheric budgets are commensurate with values reported for the tropospheric Cl and F concentrations in the early 1980s, when allowance is made for the growth rates of their source gases at the ground and the time required for tropospheric air to be transported into the stratosphere. The results are discussed with emphasis on conservation of fluorine and chlorine and the partitioning among source, sink, and reservoir gases throughout the stratosphere.  相似文献   

7.
Semi-continuous measurements of CFCl3, CF2Cl2, CCl4, CH3CCl3 and N2O were made at Adrigole, Ireland as part of the Atmospheric Lifetime Experiment (ALE). Clean, baseline air from the Atlantic Ocean was measured approximately 70% of the time; pollution events from Europe, for the remainder. The two final years of ALE data from Adrogole give a five-year record from July 1978 to June 1983. This paper extends previous work on the relative enhancements of trace gases during pollution episodes and presents (1) unambiguous identification of elevated levels of N2O concurrent with halocarbon pollution events, (2) detection of trends in emission of CH3CCl3, (3) discovery of seasonal variations in emission of CF2Cl2, CCl4 and CH3CCl3, (4) characterization of typical summer and winter pollution episodes, and (5) identification of weather patterns over Europe that are associated with high concentrations of CFCs at Adrigole. Some of these results assume that CFCl3 represents a uniform, well buffered source from the continent. The latter two results are particularly useful in the testing and calibration of three-dimensional chemical transport models. Observed enhancements are marginally consistent with estimates of halocarbon use by the chemical industry. The source of nitrous oxide correlated with halocarbons is 0.8 Tg(N)/yr from Europe alone and represents approximately 10% of the global stratospheric loss.  相似文献   

8.
The products of the Cl-atom initiated reactions of a series of hydrofluorocarbons (HFCs) and hydrochlorofluorocarbons (HCFCs) in air have been investigated at 298 K and one atmosphere (740 Torr total pressure) of air. The products observed and quantified and their yields (%) were as follows: from CHF2Cl (HCFC-22), C(O)F2 (100%); from CHFCl2 (HCFC-21), C(O)FCl (100%); from CH2FCl (HCFC-31), HC(O)F (100%); from CH3F (HFC-41), HC(O)F (100%); from CH3CFCl2 (HCFC-141b), C(O)FCl (100%); from CH3CF2Cl (HCFC-142b), C(O)F2 (100%); from CH3CHF2 (HFC-152a), C(O)F2 (92%); from CHCl2CF3 (HCFC-123), CF3C(O)Cl (98%); from CHFClCF3 (HCFC-124), CF3C(O)F (101%); and from CHF2CF3 (HFC-125), C(O)F2 (100%). The reaction mechanisms are discussed.  相似文献   

9.
A one-dimensional coupled climate and chemistry model has been developed to estimate past and possible future changes in atmospheric temperatures and chemical composition due to human activities. The model takes into account heat flux into the oceans and uses a new tropospheric temperature lapse rate formulation. As found in other studies, we estimate that the combined greenhouse effect of CH4, O3, CF2Cl2, CFCl3 and N2O in the future will be about as large as that of CO2. Our model calculates an increase in average global surface temperatures by about 0.6°C since the start of the industrial era and predicts for A.D. 2050 a twice as large additional rise. Substantial depletions of ozone in the upper stratosphere by between 25% and 55% are calculated, depending on scenario. Accompanying temperature changes are between 15°C and 25°C. Bromine compounds are found to be important, if no rigid international regulations on CFC emissions are effective. Our model may, however, concivably underestimate possible effects of CFCl3, CF2Cl2, C2F3Cl3 and other CFC and organic bromine emissions on lower stratospheric ozone, because it can not simulate the rapid breakdown of ozone which is now being observed worldwide. An uncertainty study regarding the photochemistry of stratospheric ozone, especially in the region below about 25 km, is included. We propose a reaction, involving excited molecular oxygen formation from ozone photolysis, as a possible solution to the problem of ozone concentrations calculated to be too low above 45 km. We also estimate that tropospheric ozone concentrations have grown strongly in the northern hemisphere since pre-industrial times and that further large increases may take place, especially if global emissions of NOx from fossil fuel and biomass burning were to continue to increase. Growing NOx emissions from aircraft may play an important role in ozone concentrations in the upper troposphere and low stratosphere.  相似文献   

10.
The paper presents a coupled chemical-radiative one-dimensional model which is used to assess the steady-state and time-dependent composition and temperature changes in relation to the release in the atmosphere of chemicals such as CO2, N2O, CH4, NO x and chlorofluorocarbons.The model indicates that a doubling in CO2 leads to an increase in temperature of 12.7 K near the stratopause and to an increase in total ozone of 3.3% with a local enhancement of 17% at 40 km altitude. Additional release of N2O leads to an ozone reduction in the middle stratosphere. The reduction in the ozone column is predicted to be equal to 8.8% when the amount of N2O is doubled. The chemical effect of CH4 on ozone is particularly important in the troposphere. A doubling in the mixing ratio of this gas enhances the O3 concentration by 11% at 5 km. The predicted increase of the ozone column is equal to 1.4%. A constant emission of CFCl3 (230 kT/yr) and CF2Cl2 (300 kT/yr) leads to a steady-state reduction in the ozone column of 1.9% compared to the present-day situation. The effect of some uncertainties in the chemical scheme as well as the impact of a high chlorine perturbation are briefly discussed.Finally the results of a time dependent calculation assuming a realistic scenario for the emission of chemical species are presented and analyzed.  相似文献   

11.
There are large uncertainties in identifying and quantifying the natural and anthropogenic sources of chloromethanes – methyl chloride (CH3Cl), chloroform (CHCl3) and dichloromethane (CH2Cl2), which are responsible for about 15% of the total chlorine in the stratosphere. We report two years of in situ observations of these species from the AGAGE (Advanced Global Atmospheric Gas Experiment) program at Cape Grim, Tasmania (41° S, 145° E). The average background levels of CH3Cl, CHCl3 and CH2Cl2 during 1998–2000 were 551± 8, 6.3± 0.2 and 8.9± 0.2 ppt (dry air mole fractions expressed in parts per 1012) respectively, with a two-year average amplitude of the seasonal cycles in background air of 25, 1.1 and 1.5 ppt respectively. The CH3Cl and CHCl3 records at Cape Grim show clear episodes of elevated mixing ratios up to 1300 ppt and 55 ppt respectively, which are highly correlated, suggesting common source(s). Trajectory analyses show that the sources of CH3Cl and CHCl3 that are responsible for these elevated observations are located in coastal-terrestrial and/or coastal-seawater regions in Tasmania and the south-eastern Australian mainland. Elevated levels of CH2Cl2 (up to 70 ppt above background) are associated mainly with emissions from the Melbourne/Port Phillip region, a large urban/industrial complex (population 3.5 million) 300 km north of Cape Grim.Now at the Centre for Atmospheric ChemistryNow at School of Environmental Sciences  相似文献   

12.
Methyl halides such as methyl chloride (CH3Cl) are known to be important carriers of halogen from the ocean to the atmosphere, and the halogens they release into the stratosphere by photolysis catalyze ozone depletion. Marine phytoplankton have been reported as a source of CH3Cl, but the effects of environmental temperature on the CH3Cl production by phytoplankton have not been investigated. In this study, we investigated the effects of temperature on the production of CH3Cl in the culture of a marine diatom, Phaeodactylum tricornutum CCMP 630, incubated at 10, 15, 20, 25, and 30 °C. CH3Cl concentrations in cultured samples were determined using purge and trap gas chromatograph–mass spectrometry. Phytoplankton growth was monitored by measuring the chlorophyll a concentrations. CH3Cl production was observed for several weeks at four different temperatures ranging from 10 to 25 °C. The CH3Cl production from P. tricornutum was increased with increasing temperature from 10 to 25 °C, and the maximum production rate for CH3Cl was 0.21~0.26 μmol (g chlorophyll a)?1 d?1 at 25 °C, which was several times higher than that at 10 °C (~0.03 μmol (g chlorophyll a)?1 d?1). The Arrhenius equation was successfully used to characterize the effects of temperature on the production rates of CH3Cl in the culture of P. tricornutum. Our results suggest that water temperature directly affects CH3Cl production derived from P. tricornutum and that water temperature would be a significant factor for estimating the emissions of CH3Cl from marine environments.  相似文献   

13.
A field study of trace gas emissions from biomass burning in Equatorial Africa gave methyl chloride emission ratios of 4.3×10–5±0.8×10–5 mol CH3Cl/mol CO2. Based on the global emission rates for CO2 from biomass burning we estimate a range of 226–904×109 g/y as global emission rate with a best estimate of 515×109 g/y. This is somewhat lower than a previous estimate which has been based on laboratory studies. Nevertheless, our emission rate estimates correspond to 10–40% of the global turnover of methyl chloride and thus support the importance of biomass burning as methyl chloride source. The emission ratios for other halocarbons (CH2Cl2, CHCl3, CCl4, CH3CCl3, C2HCl3, C2Cl4, F-113) are lower. In general there seems to be a substantial decrease with increasing complexity of the compounds and number of halogen atoms. For dichloromethane biomass burning still contributes significantly to the total global budget and in the Southern Hemisphere biomass burning is probably the most important source for atmospheric dichloromethane. For the global budgets of other halocarbons biomass burning is of very limited relevance.  相似文献   

14.
New laboratory measurements of NO2 absorption cross-section were performed using a Fourier transform spectrometer at 2 and 16 cm-1 (0.03 and 0.26 nm at 400 nm) in the visible range (380–830 nm) and at room temperature. The use of a Fourier transform spectrometer leads to a very accurate wavenumber scale (0.005 cm-1, 8×10-5 nm at 400 nm). The uncertainty on the new measurements is better than 4%. Absolute and differential cross-sections are compared with published data, giving an agreement ranging from 2 to 5% for the absolute values. The discrepancies in the differential cross-sections can however reach 18%. The influence of the cross-sections on the ground-based measurement of the stratospheric NO2 total amount is also investigated.  相似文献   

15.
The relative variances in stratospheric observations of longlived trace gases CH4, N2O, CF2Cl2, CFCl3 show large differences. These differences are greatly reduced when the local mean standard deviation is normalized to the local vertical gradient. This ratio, called ‘equivalent displacement height’ exhibits a characteristic vertical profile which is very similar for all the longlived trace gases, as well as for O3. With the help of this ratio, it is demonstrated that the variances are essentially due to natural causes, i.e., transport. Using the mixing length hypothesis a theoretical expression for the equivalent displacement height is derived. From it the meridional slope of the mixing surfaces and the mixing length can be calculated as function of the altitude. Additional information is obtained on the variance of that slope. The uncertainty of the measured mean trace gas profiles is defined.  相似文献   

16.
The occurrence of CH2Br2, CH2BrCl, CH2I2, CH2ClI, CHBr3, CHBr2Cl, CHBrCl2 and CH2Br-CH2Br in marine air and seawater from various sampling sites in the region of the Atlantic Ocean have been measured and evaluated. A correlation exists between high concentrations of these compounds in air and in water and the occurrence of algae at the coastlines of various islands (The Azores, Bermuda, Tenerife) and in a region of high bioactivity in the Atlantic Ocean near the West African coast.Real-world air-water concentration ratios derived from measurements in the open ocean identify the water mass near the African coast with its high primary production as a source for the above compounds. This region has to be discussed also as a possible secondary source in which CHBr2Cl, CHBrCl2 and CH2ClI can be formed via halogen-exchange. Whether CHBrCl2 and CH2ClI under-go transformation to CHCl3 and CH2Cl2, respectively, is open to further investigations.Direct photolysis and degradation by OH-radicals lead to a gradient in the marine troposphere with reduced concentrations for the organobromides above the tropospheric boundary layer.Partly presented at: 2nd International Symposium on Biosphere-Atmosphere Exchange, Mainz, F.R.Germany, 16–21 March, 1986. Part VII: Chemosphere 15 (1986) 429–436.  相似文献   

17.
Tropospheric photodissociation rate coefficients (J values) were calculated for NO2, O3, HNO2, CH2O, and CH3CHO using high spectral resolution (0.1 mm wavelength increments), and compared to the J values obtained with numerically degraded resolution (=1, 2, 4, 6, 8, and 10 nm, and several commonly used nonuniform grids). Depending on the molecule, substantial errors can be introduced by the larger increments. Thus for =10 nm, errors are less than 1% for NO2, less than 2% for HNO2, +6.5% to -16% for CH2O, -6.9% to +24% for CH3CHO, and -24% to +110% for O3. The errors for CH2O arise from the fine structure of its absorption spectrum, and are prevalently negative (underestimate of J). The errors for O3, and to a lesser extent for CH3CHO, arise mainly from under-resolving the overlap of the molecular action spectrum and the tropospheric actinic flux in the wavelength region of stratospheric ozone attenuation. The sign of those errors depends on whether the actinic flux is averaged onto the grid before or after the radiative transfer calculation. In all cases studied, grids with 2 nm produced errors no larger than 5%.  相似文献   

18.
In situ AGAGE GC-MS measurements of methyl bromide (CH3Br) and methyl chloride (CH3Cl) at Mace Head, Ireland and Cape Grim, Tasmania (1998–2001) reveal a complex pattern of sources. At Mace Head both gases have well-defined seasonal cycles with similar average annual decreases of 3.0% yr−1 (CH3Br) and 2.6% yr−1 (CH3Cl), and mean northern hemisphere baseline mole fractions of 10.37 ± 0.05 ppt and 535.7 ± 2.2 ppt, respectively. We have used a Lagrangian dispersion model and local meteorological data to segregate the Mace Head observations into different source regions, and interpret the results in terms of the known sources and sinks of these two key halocarbons. At Cape Grim CH3Br and CH3Cl also show annual decreases in their baseline mixing ratios of 2.5% yr−1 and 1.5% yr−1, respectively. Mean baseline mole fractions were 7.94 ± 0.03 ppt (CH3Br) and 541.3 ± 1.1 ppt (CH3Cl). Although CH3Cl has astrong seasonal cycle there is no well-defined seasonal cycle in the Cape Grim CH3Br record. The fact that both gases are steadily decreasing in the atmosphere at both locations implies that a change has occurred which is affecting a common, major source of both gases (possibly biomass burning) and/or their major sink process (destruction by hydroxyl radical).  相似文献   

19.
Rate constants have been measured for the gas-phase reactions of hydroxyl radical with two halons and three of their proposed substitutes and also with CHClBr-CF3 using the discharge-flow-EPR technique over the temperature range 298–460 K. The following Arrhenius expressions have been derived (units are 10–13 cm3 molecule–1 s–1): (9.3 –0.9 +1.0 ) exp{–(1326±33)/T} for CHF2Br; (7.2 –0.6 +0.7 ) exp{–(1111±32)/T} for CHFBrCF3; (8.5 –0.8 +0.9 ) exp{–(1113±35)/T} for CH2BrCF3; (12.8 –1.2 +1.5 ) exp{–(995±38)/T} for CHClBrCF3. The rate constants at 298 K have been estimated to be <2×10–17 cm3 molecule–1 s–1 for CF3Br and CF2Br—CF2Br. The atmospheric lifetimes due to hydroxyl attack have been estimated to be 5.5, 3.3, 2.8, and 1.2 years for CHF2Br, CHFBr—CF3, CH2Br—CF3 and CHClBr—CF3, respectively.  相似文献   

20.
旋转正压大气中的非线性Schrödinger方程和大气阻塞   总被引：1，自引：0，他引：1       下载免费PDF全文
本文利用WKB方法导出了旋转正压大气中的非线性Rossby波所满足的立方Schrödinger方程,指出在1≤m≤2的情况下,非线性Schrödinger方程具有包络孤立波解,同时我们还对大气中的包络Rossby孤立波的流场进行了计算,结果得到了阻塞高压和切断低压等结构,并且这些阻塞系统能够维持五天以上。  相似文献   

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