Removal of Stratospheric O3 by Radicals: In Situ Measurements of OH, HO2, NO, NO2, ClO, and BrO

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.     

Rate constants for the reactions of hydroxyl and hydroperoxyl radicals with ozone

Chain decomposition of ozone by hydroxyl and hydroperoxyl radicals has been observed. The rate constant at 3000 degrees K for OH + O(3)-->HO(2) + O(2) is 8 x 10(-14) cubic centimeters per second. The rate constant for HO(2) + O(3)--> OH + 2O(2), is 3 x 10(-15) cubic centimeters per second. These results have implications concerning stratospheric ozone.     

Role of deep cloud convection in the ozone budget of the troposphere

Convective updrafts in thunderstorms prolong the lifetime of ozone (O(3)) and its anthropogenic precursor NOx [nitric oxide (NO) + nitrogen dioxide (NO(2))] by carrying these gases rapidly upward from the boundary layer into a regime where the O(3) production efficiency is higher, chemical destruction is slower, and surface deposition is absent. On the other hand, the upper troposphere is relatively rich in O(3) and NOx from natural sources such as downward transport from the stratosphere and lightning; convective overturning conveys the O(3) and NOx toward the Earth's surface where these components are more efficiently removed from the atmosphere. Simulations with a three-dimensional global model suggest that the net result of these counteractive processes is a 20 percent overall reduction in total tropospheric O(3). However, the net atmospheric oxidation efficiency is enhanced by 10 to 20 percent.     

The hydroperoxyl radical in atmospheric chemical dynamics: reaction with carbon monoxide

From measurements of the photochemical rate of production of CO(2)(16,18) and CO(2)(16,16), produced from the low intensity photolysis of mixtures of CO, H(2)O, Ar, and O(2)(18,18), the rate constant for the reaction HO(2) + CO --> CO(2) + OH has been determined at 300 degrees K to be less than or equal to 10(-20) cubic centimeter per molecule per second. These measurements indicate that the reaction of thermalized HO(2) is of negligible importance as a sink mechanism for converting CO to CO(2) in either the troposphere or the stratosphere.     

Kinetics of the OH Reaction with Methyl Chloroform and Its Atmospheric Implications

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.     

A Reevaluation of the Ozone Budget with HALOE UARS Data: No Evidence for the Ozone Deficit

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.     

Variability in nocturnal nitrogen oxide processing and its role in regional air quality

Nitrogen oxides in the lower troposphere catalyze the photochemical production of ozone (O3) pollution during the day but react to form nitric acid, oxidize hydrocarbons, and remove O3 at night. A key nocturnal reaction is the heterogeneous hydrolysis of dinitrogen pentoxide, N2O5. We report aircraft measurements of NO3 and N2O5, which show that the N2O5 uptake coefficient, g(N2O5), on aerosol particles is highly variable and depends strongly on aerosol composition, particularly sulfate content. The results have implications for the quantification of regional-scale O3 production and suggest a stronger interaction between anthropogenic sulfur and nitrogen oxide emissions than previously recognized.     

活性氧和一氧化氮在植物-病原体互作反应中的作用

植物被病原体感染后,植物体内活性氧产量急剧增加,这一现象被称为氧爆。活性氧族包括如单线态氧^1O2、超氧阴离子自由基O2^-、氢过氧自由基HO2·、过氧化氢H2O2、羟自由基·OH等。与ROS关系密切的一氧化氮,属于活性氮族。ROS和NO参与植物生长发育调控和对环境胁迫的应答反应,特别是在对抗外来病原体的入侵的防卫过程中发挥了重要作用。本文主要讨论ROS和NO在植物与病原体相互作用中发挥的作用。     

Evidence for substantial variations of atmospheric hydroxyl radicals in the past two decades

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.     

Thunderstorms: an important mechanism in the transport of air pollutants

Acid deposition and photochemical smog are urban air pollution problems, and they remain localized as long as the sulfur, nitrogen, and hydrocarbon pollutants are confined to the lower troposphere (below about 1-kilometer altitude) where they are short-lived. If, however, the contaminants are rapidly transported to the upper troposphere, then their atmospheric residence times grow and their range of influence expands dramatically. Although this vertical transport ameliorates some of the effects of acid rain by diluting atmospheric acids, it exacerbates global tropospheric ozone production by redistributing the necessary nitrogen catalysts. Results of recent computer simulations suggest that thunderstorms are one means of rapid vertical transport. To test this hypothesis, several research aircraft near a midwestern thunderstrom measured carbon monoxide, hydrocarbons, ozone, and reactive nitrogen compounds. Their concentrations were much greater in the outflow region of the storm, up to 11 kilometers in altitude, than in surrounding air. Trace gas measurements can thus be used to track the motion of air in and around a cloud. Thunderstorms may transform local air pollution problems into regional or global atmospheric chemistry problems.     

Stratospheric hydroperoxyl measurements

The hydroperoxyl radical (HO(2)) plays a key role in stratospheric chemistry through the HOx catalytic cycle of ozone destruction. Earlier measurements of stratospheric HO(2) have given mixed results; some measured mixing ratios greatly exceed theoretical predictions. Measurements of HO(2) have now been made with a balloon-borne farinfrared spectrometer. The measured daytime profile is in excellent agreement with theory up to 40 kilometers; above this level the measurements exceed theory by 30 percent, perhaps because of underprediction of ozone at these altitudes. The nighttime HO(2) profile is strongly depressed with respect to the daytime profile, in general agreement with theory.     

Observations of ozone formation in power plant plumes and implications for ozone control strategies

Data taken in aircraft transects of emissions plumes from rural U.S. coal-fired power plants were used to confirm and quantify the nonlinear dependence of tropospheric ozone formation on plume NO(x) (NO plus NO(2)) concentration, which is determined by plant NO(x) emission rate and atmospheric dispersion. The ambient availability of reactive volatile organic compounds, principally biogenic isoprene, was also found to modulate ozone production rate and yield in these rural plumes. Differences of a factor of 2 or greater in plume ozone formation rates and yields as a function of NO(x) and volatile organic compound concentrations were consistently observed. These large differences suggest that consideration of power plant NO(x) emission rates and geographic locations in current and future U.S. ozone control strategies could substantially enhance the efficacy of NO(x) reductions from these sources.     

Coupling of nitrous oxide and methane by global atmospheric chemistry

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.     

Atmospheric halocarbons, hydrocarbons, and sulfur hexafluoride: global distributions, sources, and sinks

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.     

侧柏叶乙醇提取物抗氧化性的研究

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。     

Atmospheric Trends and Lifetime of CH3CCI3 and Global OH Concentrations

Determination of the atmospheric concentrations and lifetime of trichloroethane (CH(3)CCI(3)) is very important in the context of global change. This halocarbon is involved in depletion of ozone, and the hydroxyl radical (OH) concentrations determined from its lifetime provide estimates of the lifetimes of most other hydrogen-containing gases involved in the ozone layer and climate. Global measurements of trichloroethane indicate rising concentrations before and declining concentrations after late 1991. The lifetime of CH(3)CCI(3) in the total atmosphere is 4.8 +/- 0.3 years, which is substantially lower than previously estimated. The deduced hydroxyl radical concentration, which measures the atmosphere's oxidizing capability, shows little change from 1978 to 1994.     

Chlorine monoxide radical, ozone, and hydrogen peroxide: stratospheric measurements by microwave limb sounding

Profiles of stratospheric ozone and chlorine monoxide radical (C1O) have been obtained from balloon measurements of atmospheric limb thermal emission at millimeter wavelengths. The C1O measurements, important for assessing the predicted depletion of stratospheric ozone by chlorine from industrial sources, are in close agreement with present theory, The predicted decrease of C1O at sunset was measured. A tentative value for the stratospheric abundance of hydrogen peroxide was also determined.     

Solar cycle variability, ozone, and climate

Results from a global climate model including an interactive parameterization of stratospheric chemistry show how upper stratospheric ozone changes may amplify observed, 11-year solar cycle irradiance changes to affect climate. In the model, circulation changes initially induced in the stratosphere subsequently penetrate into the troposphere, demonstrating the importance of the dynamical coupling between the stratosphere and troposphere. The model reproduces many observed 11-year oscillations, including the relatively long record of geopotential height variations; hence, it implies that these oscillations are likely driven, at least in part, by solar variability.     

Observations of Stratospheric NO2 and O3 at Thule, Greenland

Scattered sunlight and direct light from the moon was used in two wavelength ranges to measure the total column abundances of stratospheric ozone(O(3)) and nitrogen dioxide (NO(2)) at Thule, Greenland (76.5 degrees N), during the period from 29 January to 16 February 1988. The observed O(3) column varied between about 325 and 400 Dobson units, and the lower values were observed when the center of the Arctic polar vortex was closest to Thule. This gradient probably indicates that O(3) levels decrease due to dynamical processes near the center of the Arctic vortex and should be considered in attempts to derive trends in O(3) levels. The observed NO(2) levels were also lowest in the center of the Arctic vortex and were sometimes as low as 5 x 10(14) molecules per square centimeter, which is even less than comparable values measured during Antarctic spring, suggesting that significant heterogeneous photochemistry takes place during the Arctic winter as it does in the Antarctic.     

植酸抗氧化活性的研究

[目的]研究植酸抗油脂过氧化和体外清除自由基能力。[方法]以BHT为对比,采用烘箱法测定植酸的抗油脂过氧化能力。通过Fenton反应体系产生羟自由基(.OH),由连苯三酚在碱性溶液中自氧化反应产生超氧阴离子自由基(O2-.),用分光光度法检测植酸对.OH和O2-.的作用。[结果]植酸能有效地减缓由烘箱法引发的油脂过氧化反应,效果较BHT好,且随着其浓度的增大,POV值的减少,其抗氧化效果越明显。植酸对.OH和O2-.都具有明显的清除作用,且呈一定的量效关系,对.OH和O2-.清除活性IC50值分别为2.54和9.28 mg/ml,对.OH的清除作用强于O2-.。[结论]植酸是一种较好的天然抗氧化剂和自由基清除剂。