Free Radicals Within the Antarctic Vortex: The Role of CFCs in Antarctic Ozone Loss

How strong is the case linking global release of chlorofluorocarbons to episodic disappearance of ozone from the Antarctic stratosphere each austral spring? Three lines of evidence defining a link are (i) observed containment in the vortex of ClO concentrations two orders of magnitude greater than normal levels; (ii) in situ observations obtained during ten high-altitude aircraft flights into the vortex as the ozone hole was forming that show a decrease in ozone concentrations as ClO concentrations increased; and (iii) a comparison between observed ozone loss rates and those predicted with the use of absolute concentrations of ClO and BrO, the rate-limiting radicals in an array of proposed catalytic cycles. Recent advances in our understanding of the kinetics, photochemistry, and structural details of key intermediates in these catalytic cycles as well as an improved absolute calibration for ClO and BrO concentrations at the temperatures and pressures encountered in the lower antarctic stratosphere have been essential for defining the link.     

Hydrogen radicals, nitrogen radicals, and the production of O3 in the upper troposphere

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.     

In Situ Northern Mid-Latitude Observations of ClO, O3, and BrO in the Wintertime Lower Stratosphere

In order to test photochemical theories linking chlorofluorocarbon derivatives to ozone(O(3)) depletion at high latitudes in the springtime, several related atmospheric species, including O(3), chlorine monoxide(ClO), and bromine monoxide (BrO) were measured in the lower stratosphere with instruments mounted on the NASA ER-2 aircraft on 13 February 1988. The flight path from Moffett Field, California (37 degrees N, 121 degrees W), to Great Slave Lake, Canada (61 degrees N, 115 degrees W), extended to the center of the polar jet associated with but outside of the Arctic vortex, in which the abundance of O(3) was twice its mid-latitude value, whereas BrO levels were 5 parts per trillion by volume (pptv) between 18 and 21 kilometers, and 2.4 pptv below that altitude. The ClO mixing ratio was as much as 65 pptv at 60 degrees N latitude at an altitude of 20 kilometers, and was enhanced over mid-latitude values by a factor of 3 to 5 at altitudes above 18 kilometers and by as much as a factor of 40 at altitudes below 17 kilometers. Levels of ClO and O(3) were highly correlated on all measured distance scales, and both showed an abrupt change in character at 54 degrees N latitude. The enhancement of ClO abundance north of 54 degrees N was most likely caused by low nitrogen dioxide levels in the flight path.     

Atomic Chlorine and the Chlorine Monoxide Radical in the Stratosphere: Three in situ Observations

Three simultaneous observations of atomic chlorine (Cl) and the chlorine monoxide radical (ClO) are reported which encompass the altitude interval between 25 and 45 kilometers. Together, Cl and ClO form a gas-phase catalytic cycle potentially capable of depleting stratospheric ozone. Observed Cl and C1O densities, although variable, imply that chlorine compounds constitute an important part of the stratospheric ozone budget. The results are compared with recent models of stratospheric photochemistry which have been used as a basis for predicting ozone depletion resulting from fluorocarbon release.     

Antarctic Ozone Depletion Chemistry: Reactions of N2O5 with H2O and HCl on Ice Surfaces

The reactions of dinitrogen pentoxide (N(2)O(5)) with H(2)O and hydrochloric acid (HCl) were studied on ice surfaces in a Knudsen cell flow reactor. The N(2)O(5) reacted on ice at 185 K to form condensed-phase nitric acid (HNO(3)). This reaction may provide a sink for odd nitrogen (NO(x)) during the polar winter, a requirement in nearly all models of Antarctic ozone depletion. A lower limit to the sticking coefficient, gamma, for N(2)O(5) on ice is 1 x 10(-3). Moreover, N(2)O(5) reacted on HCl-ice surfaces at 185 K, with gamma greater than 3 x 10(-3). This reaction, which produced gaseous nitryl chloride (ClNO(2)) and condensed-phase HNO(3), proceeded until all of the HCl within the ice was depleted. The ClNO(2), which did not react or condense on ice at 185 K, can be readily photolyzed in the Antarctic spring to form atomic chlorine for catalytic ozone destruction cycles. The other photolysis product, gaseous nitrogen dioxide (NO(2)), may be important in the partitioning of NO(x) between gaseous and condensed phases in the Antarctic winter.     

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.     

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.     

DOAS measurements of tropospheric bromine oxide in mid-latitudes

Episodes of elevated bromine oxide (BrO) concentration are known to occur at high latitudes in the Arctic boundary layer and to lead to catalytic destruction of ozone at those latitudes; these events have not been observed at lower latitudes. With the use of differential optical absorption spectroscopy (DOAS), locally high BrO concentrations were observed at mid-latitudes at the Dead Sea, Israel, during spring 1997. Mixing ratios peaked daily at around 80 parts per trillion around noon and were correlated with low boundary-layer ozone mixing ratios.     

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.     

O3与O3/H2O2两个体系降解除草剂2,4-D反应特性研究

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。     

The seasonal evolution of reactive chlorine in the northern hemisphere stratosphere

In situ measurements of chlorine monoxide (ClO) at mid- and high northern latitudes are reported for the period October 1991 to February 1992. As early as mid-December and throughout the winter, significant enhancements of this ozone-destroying radical were observed within the polar vortex shortly after temperatures dropped below 195 k. Decreases in ClO observed in February were consistent with the rapid formation of chlorine nitrate (ClONO(2)) by recombination of ClO with nitrogen dioxide (NO(2)) released photochemically from nitric acid (HNO(3)). Outside the vortex, ClO abundances were higher than in previous years as a result of NOx suppression by heterogeneous reactions on sulfate aerosols enhanced by the eruption of Mount Pinatubo.     

Changing composition of the global stratosphere

The current understanding of stratospheric chemistry is reviewed with particular attention to the influence of human activity. Models are in good agreement with measurements for a variety of species in the mid-latitude stratosphere, with the possible exception of ozone (O(3)) at high altitude. Rates calculated for loss of O(3) exceed rates for production by about 40 percent at 40 kilometers, indicating a possible but as yet unidentified source of high-altitude O(3). The rapid loss of O(3) beginning in the mid-1970s at low altitudes over Antarctica in the spring is due primarily to catalytic cycles involving halogen radicals. Reactions on surfaces of polar stratospheric clouds play an important role in regulating the abundance of these radicals. Similar effects could occur in northern polar regions and in cold regions of the tropics. It is argued that the Antarctic phenomenon is likely to persist: prompt drastic reduction in the emission of industrial halocarbons is required if the damage to stratospheric O(3) is to be reversed.     

Evidence for new sources of NOX in the lower atmosphere

Laboratory studies show that the reaction of short-lived O2(B3Sigmau) molecules (lifetime approximately 10 picoseconds) with N2 and the photodissociation of the N2:O2 dimer produce NOx in the stratosphere at a rate comparable to the oxidation of N2O by O(1D). This finding implies the existence of unidentified NOX sinks in the stratosphere. The NO2 observed in this experiment is isotopically heavy with a large 15N/14N enhancement. However, photodissociation of this NO2 unexpectedly produced NO molecules with a low 15N/14N ratio. The diurnal odd-nitrogen cycle in the stratosphere will be marked by a complex isotope signature that will be imprinted on the halogen and HOX catalytic cycles.     

UV dosage levels in summer: increased risk of ozone loss from convectively injected water vapor

The observed presence of water vapor convectively injected deep into the stratosphere over the United States can fundamentally change the catalytic chlorine/bromine free-radical chemistry of the lower stratosphere by shifting total available inorganic chlorine into the catalytically active free-radical form, ClO. This chemical shift markedly affects total ozone loss rates and makes the catalytic system extraordinarily sensitive to convective injection into the mid-latitude lower stratosphere in summer. Were the intensity and frequency of convective injection to increase as a result of climate forcing by the continued addition of CO(2) and CH(4) to the atmosphere, increased risk of ozone loss and associated increases in ultraviolet dosage would follow.     

The potential for ozone depletion in the arctic polar stratosphere

The nature of the Arctic polar stratosphere is observed to be similar in many respects to that of the Antarctic polar stratosphere, where an ozone hole has been identified. Most of the available chlorine (HCl and ClONO(2)) was converted by reactions on polar stratospheric clouds to reactive ClO and Cl(2)O(2) throughout the Arctic polar vortex before midwinter. Reactive nitrogen was converted to HNO(3), and some, with spatial inhomogeneity, fell out of the stratosphere. These chemical changes ensured characteristic ozone losses of 10 to 15% at altitudes inside the polar vortex where polar stratospheric clouds had occurred. These local losses can translate into 5 to 8% losses in the vertical column abundance of ozone. As the amount of stratospheric chlorine inevitably increases by 50% over the next two decades, ozone losses recognizable as an ozone hole may well appear.     

Mn2+催化臭氧化去除腐殖酸的试验研究

以天然水体中常见的金属离子Mn2+为催化剂,研究了其对水中溶解性腐殖酸的催化臭氧化效能.结果表明,Mn2+对臭氧化去除腐殖酸有明显的催化作用,反应25 min,对腐殖酸的去除率可达82.3%,较单独臭氧化提高了24.3%;通过Na2CO3对催化反应的影响验证了Mn2+催化臭氧化反应遵循自由基反应原理;同时也发现催化效率随着臭氧流量的增大而提高,随着pH值的升高而提高;且少量Mn2+投加即可产生明显的催化作用,过量则会产生抑制作用.     

Ca（ClO）_2和O_3组合去除多菌灵残留的研究

[目的]探讨次氯酸钙和臭氧组合的诸因素对去除金橘多菌灵残留的影响。[方法]采用Box-Behnken响应面设计方法（response surface methodology,RSM）开展了多菌灵初始浓度、次氯酸钙水溶液浸泡时间、臭氧水浸泡时间、次氯酸钙浓度等因素对去除金橘多菌灵残留作用的研究。[结果]在试验选取的区间内,各因素对去除金橘多菌灵残留作用由大到小依次为臭氧水溶液浸泡时间、次氯酸钙水溶液浸泡时间、多菌灵初始残留量和次氯酸钙溶液浓度。对试验结果进行拟合得到了金橘多菌灵残留量与上述各因素关系的二次多项式模型,验证试验结果表明模型具有较高的精确度。[结论]该模型可以用于指导在确定多菌灵初始浓度和残留限值条件下,采取恰当的次氯酸钙溶液浸泡时间、臭氧水浸泡时间、次氯酸钙浓度等综合处理措施,以保证获得期望的多菌灵残留限值。     

Gaseous nitrate radical: possible nighttime atmospheric sink for biogenic organic compounds

The gaseous nitrate (NO(3)) radical, which has recently been measured in nighttime ambient atmospheres over the United States and Europe at concentrations up to approximately 350 parts per trillion, has now been shown to react rapidly with the biogenically emitted organic compounds dimethyl sulfide (DMS), isoprene, and several monoterpenes. Computer simulations demonstrate that these reactions can dominate the atmospheric behavior of these organic compounds at night. Thus reaction with NO(3) radicals may be the unknown, nonphotochemical removal process for DMS recently invoked by Andreae and Raemdonck to explain the absence of a diurnal profile for DMS in maritime air influenced by continental air masses. Similarly, the nighttime reaction of NO(3) radicals with monoterpenes can be a dominant removal process, leading to very low monoterpene concentrations in ambient atmospheres during the early morning.     

光照对分蘖期水稻叶际及根系-培养液体系 N2O 和 NOX（NO，NO2）排放的影响

[目的]该研究探讨光照对分蘖期水稻根、叶界面N2O和NOX排放的作用及其机制。[方法]试验在水培控氮、小型光控培养箱控光和同步测定条件下,探讨了不同光质、光强及光控处理对分蘖期水稻叶际及根系-培养液体系 N2O和 NOX 排放的影响。[结果]①在相同氮源(NH4NO3-N,90 mg/L)、日间光照为6000、8000 lx条件下,分蘖期平均水稻叶际 N2O和NO排放速率分别为27.08、32.33μg/(pot·h)和0.114、0.057μg/(pot·h),分别占 N2O和 NO总排放的57.38%、58.65%和9.65%、4.52%,水稻叶际是N2O的重要排放源;②在光强(1600 lx)一致条件下,LED黄、绿、白、红、蓝光处理的平均水稻叶际N2O 排放速率分别为6.83、9.40、9.73、2.82和4.08μg/(pot·h),光 X强较高的红(3000 lx)、蓝光(2500 lx)处理能同步抑制分蘖期水稻根、叶界面N2O的挥发(P<0.01),LED红、白光有促进日间水稻叶际NO排放的作用,LED蓝光则有同步抑制水稻根、叶界面 NO挥发的作用效果,但不同光控处理下水稻根、叶界面均无明显的NO2净排放作用;③0~8000 lx 范围内随着光照增强,水稻根部NO及根、叶界面 N2O排放同步增加,但高光强(6000~8000 lx)下水稻叶际 NO排放显著大幅下降(P<0.01)。[结论]水稻根、叶界面均以N2O挥发为主;试验供氮水平下适度控制日间光强并同步增加红光、蓝光比例的技术,能同步抑制水稻根、叶界面氮氧化物的排放。     

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。