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1.
The rate coefficients for the reaction of hydroxyl (OH) radicals with methyl chloroform (CH(3)CCI(3)) were measured between 243 and 379 kelvin with the pulsed photolysis-laserinduced fluorescence method. The measured rate coefficients at 298 and 277 kelvin were approximately 20 and approximately 15%, respectively, lower than earlier values. These results will increase the tropospheric OH concentrations derived from the CH(3)CCI(3) budget analysis by approximately 15%. The predicted atmospheric lifetimes of species whose main loss process is the reaction with OH in the troposphere will be lowered by 15% with consequent changes in their budgets, global warming potentials, and ozone depletion potentials.  相似文献   

2.
Nitrous oxide (N(2)O) and methane (CH(4)) are chemically reactive greenhouse gases with well-documented atmospheric concentration increases that are attributable to anthropogenic activities. We quantified the link between N(2)O and CH(4) emissions through the coupled chemistries of the stratosphere and troposphere. Specifically, we simulated the coupled perturbations of increased N(2)O abundance, leading to stratospheric ozone (O(3)) depletion, altered solar ultraviolet radiation, altered stratosphere-to-troposphere O(3) flux, increased tropospheric hydroxyl radical concentration, and finally lower concentrations of CH(4). The ratio of CH(4) per N(2)O change, -36% by mole fraction, offsets a fraction of the greenhouse effect attributable to N(2)O emissions. These CH(4) decreases are tied to the 108-year chemical mode of N(2)O, which is nine times longer than the residence time of direct CH(4) emissions.  相似文献   

3.
The concentrations of the hydrogen radicals OH and HO2 in the middle and upper troposphere were measured simultaneously with those of NO, O3, CO, H2O, CH4, non-methane hydrocarbons, and with the ultraviolet and visible radiation field. The data allow a direct examination of the processes that produce O3 in this region of the atmosphere. Comparison of the measured concentrations of OH and HO2 with calculations based on their production from water vapor, ozone, and methane demonstrate that these sources are insufficient to explain the observed radical concentrations in the upper troposphere. The photolysis of carbonyl and peroxide compounds transported to this region from the lower troposphere may provide the source of HOx required to sustain the measured abundances of these radical species. The mechanism by which NO affects the production of O3 is also illustrated by the measurements. In the upper tropospheric air masses sampled, the production rate for ozone (determined from the measured concentrations of HO2 and NO) is calculated to be about 1 part per billion by volume each day. This production rate is faster than previously thought and implies that anthropogenic activities that add NO to the upper troposphere, such as biomass burning and aviation, will lead to production of more O3 than expected.  相似文献   

4.
The hydroxyl radical (OH) is the dominant oxidizing chemical in the atmosphere. It destroys most air pollutants and many gases involved in ozone depletion and the greenhouse effect. Global measurements of 1,1,1-trichloroethane (CH3CCl3, methyl chloroform) provide an accurate method for determining the global and hemispheric behavior of OH. Measurements show that CH3CCl3 levels rose steadily from 1978 to reach a maximum in 1992 and then decreased rapidly to levels in 2000 that were lower than the levels when measurements began in 1978. Analysis of these observations shows that global OH levels were growing between 1978 and 1988, but the growth rate was decreasing at a rate of 0.23 +/- 0.18% year(-2), so that OH levels began declining after 1988. Overall, the global average OH trend between 1978 and 2000 was -0.64 +/- 0.60% year(-1). These variations imply important and unexpected gaps in current understanding of the capability of the atmosphere to cleanse itself.  相似文献   

5.
O3与O3/H2O2两个体系降解除草剂2,4-D反应特性研究   总被引：4，自引：3，他引：4  
分别采用O3、O3/H2O2体系降解苯氧羧酸类除草剂2,4-D,探讨了降解过程中反应温度、pH值、O3混合气流量、有机物初始浓度等操作条件的变化对降解动力学的影响。结果发现,温度和pH值的影响较大,O3流量影响最小,温度升高、pH值增大、臭氧流量增加、2,4-D初始浓度降低均有助于降解速率的提高。O3/H2O2体系中,H2O2能促进O3分解产生大量自由基,导致2,4-D反应活化能降低。和O3相比,O3/H2O2体系降解效果好,降解时间短,反应条件温和,操作费用低,是很有发展前景的高级氧化技术。  相似文献   

6.
Frequent atmospheric measurements of the anthropogenic compound methylchloroform that were made between 1978 and 1985 indicate that this species is continuing to increase significantly around the world. Reaction with the major atmospheric oxidant, the hydroxyl radical (OH), is the principal sink for this species. The observed mean trends for methylchloroform are 4.8, 5.4, 6.4, and 6.9 percent per year at Aldrigole (Ireland) and Cape Meares (Oregon), Ragged Point (Barbados), Point Matatula (American Samoa), and Cape Grim (Tasmania), respectively, from July 1978 to June 1985. These measured trends, combined with knowledge of industrial emissions, were used in an optimal estimation inversion scheme to deduce a globally averaged methylchloroform atmospheric lifetime of 6.3 (+ 1.2, -0.9) years (1sigma uncertainty) and a globally averaged tropospheric hydroxyl radical concentration of (7.7 +/- 1.4) x 10(5) radicals per cubic centimeter (1sigma uncertainty). These 7 years of gas chromatographic measurements, which comprise about 60,000 individual calibrated real-time air analyses, provide the most accurate estimates yet of the trends and lifetime of methylchloroform and of the global average for tropospheric hydroxyl radical levels. Accurate determination of hydroxyl radical levels is crucial to understanding global atmospheric chemical cycles and trends in the levels of trace gases such as methane.  相似文献   

7.
The gaseouis plume from an isolated 1000-megawatt power plant was systematically examined from a single engine aircraft to determine the extent to which NO(x) and SO(2), chemistry occurs as a function of distance. The concentrations of ambient ozone, water vapor, and hydroxyl free radicals are indicated to be of major importance in defining the chemistry of power plant plumes during summertime conditions.  相似文献   

8.
Simultaneous in situ measurements of the concentrations of OH, HO(2), ClO, BrO, NO, and NO(2) demonstrate the predominance of odd-hydrogen and halogen free-radical catalysis in determining the rate of removal of ozone in the lower stratosphere during May 1993. A single catalytic cycle, in which the rate-limiting step is the reaction of HO(2) with ozone, accounted for nearly one-half of the total O(3) removal in this region of the atmosphere. Halogen-radical chemistry was responsible for approximately one-third of the photochemical removal of O(3); reactions involving BrO account for one-half of this loss. Catalytic destruction by NO(2), which for two decades was considered to be the predominant loss process, accounted for less than 20 percent of the O(3) removal. The measurements demonstrate quantitatively the coupling that exists between the radical families. The concentrations of HO(2) and ClO are inversely correlated with those of NO and NO(2). The direct determination of the relative importance of the catalytic loss processes, combined with a demonstration of the reactions linking the hydrogen, halogen, and nitrogen radical concentrations, shows that in the air sampled the rate of O(3) removal was inversely correlated with total NOx, loading.  相似文献   

9.
Concentrations of the halocrbons CCl(3)F (F-11), CCl(2)F(2) (F-12), CCl(4), and CH(3)CCl(3), methane (CH(4)), and nitrous oxide (N(2)O) 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 CH(3)CCl(3) 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 CH(3)CC1(3) 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.  相似文献   

10.
Dramatic declines in emissions of methyl chloroform (1,1, 1-trichloroethane) resulting from the Montreal Protocol provide an unprecedented opportunity to improve our understanding of the oxidizing power of Earth's atmosphere. Atmospheric observations of this industrial gas during the late 1990s yield new insights into the global burden and distribution of the hydroxyl radical. Our results set firm upper limits on the global and Southern Hemispheric lifetimes of methyl chloroform and confirm the predominance of hydroxyl in the tropics. Our analysis suggests a global lifetime for methyl chloroform of 5.2 (+0.2, -0.3) years, a Southern Hemispheric lifetime of 4.9 (+0.2, -0.3) years, and mean annual concentrations of OH that are 15 +/- 10% higher south of the intertropical convergence zone than those north of this natural mixing boundary between the hemispheres.  相似文献   

11.
Alkane hydrocarbons (propane, isobutane, and n-butane) from liquefied petroleum gas (LPG) are present in major quantities throughout Mexico City air because of leakage of the unburned gas from numerous urban sources. These hydrocarbons, together with olefinic minor LPG components, furnish substantial amounts of hydroxyl radical reactivity, a major precursor to formation of the ozone component of urban smog. The combined processes of unburned leakage and incomplete combustion of LPG play a significant role in causing the excessive ozone characteristic of Mexico City. Reductions in ozone levels should be possible through changes in LPG composition and lowered rates of leakage.  相似文献   

12.
The atmospheric residence time for methyl bromide (CH3Br) has been estimated as 0.8 +/- 0.1 years from its empirical spatial variability relative to C2H6, C2Cl4, CHCl3, and CH3Cl. This evaluation of the atmospheric residence time, based on Junge's 1963 general proposal, provides an estimate for CH3Br that is independent of source and sink estimates. Methyl bromide from combined natural and anthropogenic sources furnishes about half of the bromine that enters the stratosphere, where it plays an important role in ozone destruction. This residence time is consistent with the 0.7-year value recently calculated for CH3Br from the combined strength estimates for its known significant sinks.  相似文献   

13.
The treatment of agricultural soils with CH(3)Br (MeBr) has been suggested to be a significant source of atmospheric MeBr which is involved in stratospheric ozone loss. A field fumigation experiment showed that, after 7 days, 34 percent of the applied MeBr had escaped into the atmosphere. The remaining 66 percent should have caused an increase in bromide in the soil; soil bromide increased by an amount equal to 70 percent of the applied MeBr, consistent with the flux measurements to within 4 percent. Comparison with an earlier experiment in which the escape of MeBr to the atmosphere was greater showed that higher soil pH, organic content and soil moisture, and deeper, more uniform injection of MeBr may in combination reduce the escape of MeBr.  相似文献   

14.
The oxidizing capacity of the global atmosphere is largely determined by hydroxyl (OH) radicals and is diagnosed by analyzing methyl chloroform (CH(3)CCl(3)) measurements. Previously, large year-to-year changes in global mean OH concentrations have been inferred from such measurements, suggesting that the atmospheric oxidizing capacity is sensitive to perturbations by widespread air pollution and natural influences. We show how the interannual variability in OH has been more precisely estimated from CH(3)CCl(3) measurements since 1998, when atmospheric gradients of CH(3)CCl(3) had diminished as a result of the Montreal Protocol. We infer a small interannual OH variability as a result, indicating that global OH is generally well buffered against perturbations. This small variability is consistent with measurements of methane and other trace gases oxidized primarily by OH, as well as global photochemical model calculations.  相似文献   

15.
The elusive protonated ozone ion (O(3)H(+)) has been long postulated as a reactive intermediate but never experimentally observed. This ion has been detected here in mass spectrometric experiments with the use of Fourier transform ion cyclotron resonance. In these experiments, ozone (O(3)) was protonated by strong acids-for example, H(3)(+), KrH(+), XeH(+), and CH(5)(+). The hitherto experimentally unknown proton affinity of O(3) was evaluated by a "bracketing" technique and determined to be 148 -/+ 3 kilocalories mole(-1) at 298 kelvin, in excellent agreement with a value determined in a recent theoretical study of the O(3)/O(3)H(+) system, which was 148 kilocalories mole(-1) at zero temperature ( approximately 149.5 kilocalories mole(-1) at 298 kelvin).  相似文献   

16.
The global distribution of fluorocarbon-12 and fluorocarbon-11 is used to establish a relatively fast interhemispheric exchange rate of 1 to 1.2 years. Atmospheric residence times of 65 to 70 years for fluorocarbon-12 and 40 to 45 years for fluorocarbon-l1 best fit the observational data. These residence times rule out the possibility of any significant missing sinks that may prevent these fluorocarbons from entering the stratosphere. Atmospheric measurements of methyl chloroform support an 8-to 10-year residence time and suggest global average hydroxyl radical (HO) concentrations of 3 x 10(5) to 4 x 10(5) molecules per cubic centimeter. These are a factor of 5 lower than predicted by models. Additionally, methyl chloroform global distribution supports Southern Hemispheric HO levels that are a factor of 1.5 or more larger than the Northern Hemispheric values. The long residence time and the rapid growth of methyl chloroform cause it to be a potentially significant depleter of stratospheric ozone. The oceanic sink for atmospheric carbon tetrachloride is about half as important as the stratospheric sink. A major source of methyl chloride (3 x 10(12)grams per year), sufficient to account for nearly all the atmospheric methyl chloride, has been identified in the ocean.  相似文献   

17.
Recently, additional ozone production mechanisms have been proposed to resolve the ozone deficit problem, which arises from greater ozone destruction than production in several photochemical models of the upper stratosphere and lower mesosphere. A detailed ozone model budget analysis was performed with simultaneous observations of O(3), HCl, H(2)O, CH(4), NO, and NO(2) from the Halogen Occultation Experiment (HALOE) on the Upper Atmosphere Research Satellite (UARS) under conditions with the strongest photochemical control of ozone. The results indicate that an ozone deficit may not exist. On the contrary, the use of currently recommended photochemical parameters leads to insufficient ozone destruction in the model.  相似文献   

18.
采用分光光度法测定不同质量浓度的侧柏叶乙醇提取物对羟基自由基、超氧自由基的清除能力及其还原能力。结果表明:随着侧柏叶乙醇提取物质量浓度的增加,还原能力、清除羟基自由基和超氧自由基能力都随着增强,所有提取物清除羟基自由基的活性均高于超氧自由基。此外在高实验质量浓度下,50%乙醇提取物清除羟基自由基的能力最强,还原能力和清除超氧自由基的能力由强到弱依次为50%乙醇提取物、95%乙醇提取物、70%乙醇提取物。  相似文献   

19.
Surface waters along a cruise track in the East Pacific Ocean were undersaturated in methyl bromide (CH(3)Br) in most areas except for coastal and upwelling regions, with saturation anomalies ranging from + 100 percent in coastal waters to -50 percent in open ocean areas, representing a regionally weighted mean of -16 (-13 to -20) percent. The partial lifetime of atmospheric CH(3)Br with respect to calculated oceanic degradation along this cruise track is 3.0 (2.9 to 3.6) years. The global, mean dry mole fraction of CH3Br in the atmosphere was 9.8 +/- 0.6 parts per trillion, with an interhemispheric ratio of 1.31 +/- 0.08. These data indicate that approximately 8 percent (0.2 parts per trillion) of the observed interhemispheric difference in atmospheric CH3Br could be attributed to an uneven global distribution of oceanic sources and sinks.  相似文献   

20.
为了测定金佛手果叶黄酮的体外抗氧化能力,以金佛手果、叶为试材,测定果叶黄酮对O2-,·OH和DPPH的清除率.结果表明,果、叶黄酮对DPPH的清除能力IC50分别为8.25,9.03mg·L-1,稍弱于Vc和芦丁;对O2-清除能力IC50分别为17.74,20.77mg·L1,但强于芦丁,弱于Vc;对·OH清除能力IC50分别为17.06,15.86mg·L-1,清除能力强于Vc,与芦丁相差无几.方差分析显示,不同浓度果叶黄酮对O2-,·OH清除率差异极显著,且随着在反应液中浓度的增加,果叶黄酮对O2-清除率呈上升趋势,但达一定浓度时,清除率趋于平缓.果叶黄酮对·OH体系最佳作用剂量为18mg·L-1.  相似文献   

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