平流层臭氧非线性响应的机理研究

完善了王革丽和杨培才(2007)建立的平流层下部臭氧异相光化学反应箱式模式,在原有模式基础上加入溴族,研究了平流层下部臭氧对硫酸气溶胶表面积浓度与氯化物、溴化物以及氮氧化物的排放强度变化的非线性响应,理解平流层臭氧对人类活动的依赖性.结果表明,当氯化物排放强度偏离当前水平时,气溶胶可以通过与溴化物、氯化物、氮氧化物之间的相互作用,干预光化系统的非线性行为,改变系统在参数空间中的拓扑结构.     

基于层积云飞机观测资料评估气溶胶间接效应

利用2009年4、5月美国浅薄低云观测项目(RACORO)的层积云飞机观测资料,使用两种方法对气溶胶间接效应进行了估算:根据云滴数浓度定义的值(AIE_n)和根据有效半径定义的值(AIE_s)。AIE_n几乎都比AIE_s大,尤其在中等含水量条件下。理论推导表明,AIE_n与AIE_s的偏差应与气溶胶对云滴谱离散度的影响有关,即离散度效应。当AIE_n加上离散度效应后,数值与AIE_s十分接近,证实了理论预期。离散度效应对气溶胶间接效应的贡献主要为抵消作用,这种抵消作用在中等含水量时最大,当含水量为0.24 g/m~3时达到37%左右。该研究成果增强了对气溶胶-云相互作用的理论认识,将有助于增强对模式和观测中气溶胶间接效应的准确评估。     

Minor Constituent Concentrations Measured from a High Altitude Aircraft Using High Resolution Far-Infrared Fourier Transform Spectroscopy

Far-infrared emission spectroscopy has beendemonstrated to be a valuable method for remotesensing of trace species in the stratosphere, with theability to simultaneously detect a number of keychemical species. SAFIRE-A is a new far-infraredFourier Transform (FT) spectrometer which has beenspecifically designed to operate on board of a highaltitude aircraft in the lower stratosphere and uppertroposphere regions where relatively few remotesensing measurements have been made. Using newtechnology, the sensitivity of the FT spectrometermethod has been substantially improved for the longwavelength region. Results are reported formeasurements of O₃, HNO₃ and N₂O at 17and 19 km using a detection window near 23 cm^-1.Geographical and altitude variability of the volumemixing ratio of these constituents and their relativecorrelation are discussed. Ozone measurements agreewell with in situ measurements, except in regions ofstrong stirring and mixing associated with deformationof the northern vortex edge. Whilst SAFIREmeasurements of trace gases do not capture all of thelocal variability seen by rapid in-situ techniques,they can indicate horizontal variability close to, butnot intercepted by, the aircraft's flight path. Apossible detection of ClO at the low background levelsexpected outside the polar vortex is also reported.     

The origin of ozone-rich air in the middle stratosphere observed over Europe at the end of January 1979

Daily ozone soundings over Switzerland in the winter of 1979 showed, at the end of January some extremely high values of the ozone mixing ration around the 10 mb level-9 to 10 ppm compared with a climatological mean of 6 ppm. At the same time, the temperature and ozone mixing ratio was measured by the LIMS experiment (Limb Infrared Monitor of the Stratosphere) on Nimbus 7. The single LIMS ozone profiles, as well as the LIMS 10 mb ozone maps, also showed extreme ozone maxima. Ozone transport was investigated by trajectory computations based on the LIMS geopotential height fields. Displacements and deformations of air parcel chains in 48 h were used to construct ozone maps, using the distribution on a previous day. The correspondence of such kinematically-constructed ozone maps using the actual LIMS maps is striking. This method is, thus, a strong indication of the self-consistency of the different LIMS products (ozone, temperature, geopotential) and explains the unusual ozone observations.     

Laboratory Studies of Bromide Oxidation in the Presence of Ozone: Evidence for a Glass-Surface Mediated Reaction

The reaction of sodium bromide particles in the presence of ozone was studied in a flow system both under dark conditions and with 254 nm radiation. We found that there was significant formation of gaseous bromine (probably Br₂) in the presence of ozone in the dark, and that bromide deposited to the walls of the Pyrex reaction flask was its source. The observed rate of gaseous bromine formation in these experiments was approximately 100–1000 times faster than expected based on the knownrate constant for aqueous reaction of bromide with ozone. While the mechanism responsible for this enhanced reactivity was not identified, based on previous reports we suggest that the glass surface converted ozone to more reactive species, such as hydroxyl radical, which in turn oxidized bromide. In the presence of 254 nm radiation, rates of gaseous bromine collection were further enhanced, likely as a result of increased radical production in the system, and wall-deposited bromide was also the source of the gaseous bromine. In these `light' experiments, there was a significant decline in ozone mixing ratios, consistent with bromine radical chemistry. These results suggest the possibility that ozone reacting with internally mixed silicate/sea-salt particles might be a significant mechanism for the oxidation of particulate halides, and subsequent release of photoactive halogen species, in the marine boundary layer.     

Extremely low temperatures in the stratosphore and very low total ozone amount above northern and central Europe during winter 1989

On 1 February 1989, -83.5°C was recorded in 27.8 hPa over Hohenpeißenberg, the lowest temperature in the 22-year series. This was measured together with a very low total ozone amount of 266 DU. This may be compared with nearly twice this amount on 27 February 1989. The situation was very unusual: following an extremely cold winter in the Arctic stratosphere, the stratospheric cold pole was located over southern Scandinavia on 1 February in a very southerly position. The analyzed temperatures of -92 °C in 30 hPa were also unusual. Even though the low ozone amounts over Hohenpeißenberg were probably dynamically caused, an additional very small ozone decrease due to heterogeneous reactions in altitudes from 23–28 km, where the temperatures lie below -80 °C, cannot be ruled out. Extinction measurements by the orbitting SAGE II instrument indeed show polar stratospheric clouds over Europe near 50° N during the period 31 January–2 February. Also, polar stratospheric clouds were previously observed over Kiruna at similarly low temperatures and signs of a corresponding small ozone decrease were noted there.     

2008年冬季北京上空上对流层/下平流层臭氧的异常特征

利用国产GPSO3臭氧探空系统观测的大气臭氧探空资料和NCEP再分析资料,结合对天气形势、大气环流背景、高空位涡变化及对流层顶高度扰动的分析,深入研究了2008年冬季北京地区10~14 km高度范围内持续出现的臭氧次峰值及大气臭氧含量异常现象。结果表明:在2008年我国南方雪灾这一特殊时期,引起臭氧垂直分布持续出现次峰值现象及臭氧含量异常的主要原因是平流层空气强烈下沉运动及其与对流层的交换作用,而引起这种下沉运动及平流层-对流层交换则是由于该阶段特殊的天气背景,乌拉尔阻塞高压长时间维持,贝加尔湖到巴尔喀什湖一带横槽稳定存在,里海以东切断低压长期维持,造成冷空气长时间、稳定地南下影响北京上空臭氧的垂直分布。加之副热带急流的出现,北京正处于其入口区左侧,其上空有强烈的辐合下沉运动,有利于平流层空气向下输送。此次臭氧次峰值及臭氧含量异常的现象很好地说明,在冷空气天气过程的影响下,北京地区上空的平流层空气运动及其与对流层的交换十分活跃。     

Impact of increasing stratospheric water vapor on ozone depletion and temperature change

Using a detailed, fully coupled chemistry climate model (CCM), the effect of increasing stratospheric H_{2O on ozone and temperature is investigated. Different CCM time-slice runs have been performed to investigate the chemical and radiative impacts of an assumed 2 ppmv increase in H2O. The chemical effects of this H2O increase lead to an overall decrease of the total column ozone (TCO) by ～1% in the tropics and by a maximum of 12% at southern high latitudes. At northern high latitudes, the TCO is increased by only up to 5% due to stronger transport in the Arctic. A 2-ppmv H2O increase in the model's radiation scheme causes a cooling of the tropical stratosphere of no more than 2 K, but a cooling of more than 4 K at high latitudes. Consequently, the TCO is increased by about 2%--6%. Increasing stratospheric H2O, therefore, cools the stratosphere both directly and indirectly, except in the polar regions where the temperature responds differently due to feedbacks between ozone and H2O changes. The combined chemical and radiative effects of increasing H2O may give rise to more cooling in the tropics and middle latitudes but less cooling in the polar stratosphere. The combined effects of H2O increases on ozone tend to offset each other, except in the Arctic stratosphere where both the radiative and chemical impacts give rise to increased ozone. The chemical and radiative effects of increasing H2O cause dynamical responses in the stratosphere with an evident hemispheric asymmetry. In terms of ozone recovery, increasing the stratospheric H2O is likely to accelerate the recovery in the northern high latitudes and delay it in the southern high latitudes. The modeled ozone recovery is more significant between 2000--2050 than between 2050--2100, driven mainly by the larger relative change in chlorine in the earlier period.}     

平流层大气环流的典型系统及变化特征综述

随着大气探测技术以及计算机性能的不断提高,近年来平流层探测数据日渐丰富,中层大气模式也得到了快速发展,平流层中一些重要的物理、化学以及动力过程得以深入研究,对平流层大气环流的认识也进一步加深。本文分析了平流层准2 a振荡（Quasi-Biennial Oscillation,QBO）、平流层残余（Brewer-Dobson,BD）环流和平流层极地环流等主要的平流层大气环流系统和信号的气候态特征、形成机制、年际变率以及长期趋势等,阐述了它们的主要影响因子和过程,讨论并展望了与平流层环流有关的一些主要科学问题。     

The Effect of Super Volcanic Eruptions on Ozone Depletion in a Chemistry–Climate Model

With the gradual yet unequivocal phasing out of ozone depleting substances(ODSs), the environmental crisis caused by the discovery of an ozone hole over the Antarctic has lessened in severity and a promising recovery of the ozone layer is predicted in this century. However, strong volcanic activity can also cause ozone depletion that might be severe enough to threaten the existence of life on Earth. In this study, a transport model and a coupled chemistry–climate model were used to simulate the impacts of super volcanoes on ozone depletion. The volcanic eruptions in the experiments were the 1991 Mount Pinatubo eruption and a 100 × Pinatubo size eruption. The results show that the percentage of global mean total column ozone depletion in the 2050 RCP8.5 100 × Pinatubo scenario is approximately 6% compared to two years before the eruption and 6.4% in tropics. An identical simulation, 100 × Pinatubo eruption only with natural source ODSs, produces an ozone depletion of 2.5% compared to two years before the eruption, and with 4.4% loss in the tropics. Based on the model results,the reduced ODSs and stratospheric cooling lighten the ozone depletion after super volcanic eruption.     

热带平流层臭氧准两年周期振荡的特征及数值模拟

利用HALOE的观测资料、对热带地区平流层臭氧垂直分布的年际变化及其准两年周期振荡（QBO）进行研究，并同赤道上空平均的纬向风场的准两年周期振荡进行了模拟研究。资料分析结果表明，平流层臭氧浓度高值区的位置在南北方向上和垂直方向上的有明显的准两年周期，臭氧浓度高值中心的南北移动和上下移动又引起局地臭氧总量的周期性变化和准两年周期振荡南北半球不对称。而臭氧浓度中心位置的准两年周期变化与赤道上空平均纬向风的准两年周期振荡密切相关。资料分析还表明，赤道上空平流层中臭氧浓度QBO的位相随高度变化多次。模拟试验表明，纬向风QBO引起垂直经圈环流的变化，在平流层有三对余差环流圈。它们对O3在不同纬度和高度的输送是引起O3准两年周期振荡的重要动力原因。其中，余差环流在平流层中层（25－35km)的环流圈起着重要的作用。     

华东高海拔地区夏季气溶胶数浓度及谱分布特征

利用2014年7月黄山光明顶观测获得的气溶胶数浓度、气溶胶数谱数据,对黄山夏季气溶胶数浓度及谱分布特征进行分析,并在此基础上对气溶胶数谱进行了对数正态分布拟合。研究结果表明:黄山夏季气溶胶平均数浓度约为3 518.27 cm~(-3),主要集中在爱根核模态;气溶胶平均数浓度日变化呈双峰分布,峰值浓度的出现伴随着小粒子的增多。气溶胶数浓度与相对湿度和风速成负相关,高浓度的气溶胶多出现在较弱的东南风时;积聚模态气溶胶数浓度受风向影响显著。不同气团背景下气溶胶数谱差异集中在小于100 nm和500~1 000 nm粒径范围。爱根核模态气溶胶在高湿的西南气团影响下数浓度最低、谱较窄,而高温、低湿的东南气团对应的气溶胶数浓度最高、谱最宽,北方气团对应的气溶胶数浓度和谱宽居中;500~1 000 nm粒径范围气溶胶数谱分布特征与之相反。不同背景的气溶胶数谱和体积谱均可采用爱根模态、积聚模态1和积聚模态2三个模态进行对数正态分布拟合,但不同气团背景下的各模态谱型参数差异较大。     

Iodine Chemistry and its Role in Halogen Activation and Ozone Loss in the Marine Boundary Layer: A Model Study

A detailed set of reactions treating the gas and aqueous phase chemistry of the most important iodine species in the marine boundary layer (MBL) has been added to a box model which describes Br and Cl chemistry in the MBL. While Br and Cl originate from seasalt, the I compounds are largely derived photochemically from several biogenic alkyl iodides, in particular CH2I2, CH2ClI, C2H5I, C3H7I, or CH3I which are released from the sea. Their photodissociation produces some inorganic iodine gases which can rapidly react in the gas and aqueous phase with other halogen compounds. Scavenging of the iodine species HI, HOI, INO2, and IONO2 by aerosol particles is not a permanent sink as assumed in previous modeling studies. Aqueous-phase chemical reactions can produce the compounds IBr, ICl, and I2, which will be released back into the gas phase due to their low solubility. Our study, although highly theoretical, suggests that almost all particulate iodine is in the chemical form of IO-3. Other aqueous-phase species are only temporary reservoirs and can be re-activated to yield gas phase iodine. Assuming release rates of the organic iodine compounds which yield atmospheric concentrations similar to some measurements, we calculate significant concentrations of reactive halogen gases. The addition of iodine chemistry to our reaction scheme has the effect of accelerating photochemical Br and Cl release from the seasalt. This causes an enhancement in ozone destruction rates in the MBL over that arising from the well established reactions O(1D) + H2O 2OH, HO2 + O3 OH + 2O2, and OH + O3 HO2 + O2. The given reaction scheme accounts for the formation of particulate iodine which is preferably accumulated in the smaller sulfate aerosol particles.     

近30a北极平流层臭氧的季节和年际变化特征

综合利用1978-2011年TOMS（Total Ozone Mapping Spectrometer）和OMI（Ozone Monitoring Instrument）臭氧总量资料,MLS（Microwave Limb Sounder）臭氧廓线资料以及NCEP/NCAR再分析气象场资料,对比研究了近30a南北极臭氧总量的年际变化和季节变化差异,重点分析了2010/2011年冬末春初北极臭氧出现的异常损耗现象,探讨北极春季臭氧低值产生的原因。结果表明：与南极地区一年四季都保持一个臭氧低值中心明显不同,北极臭氧总量的减少则是伴随着整个春夏季（4-8月）,在秋季（10月）达到最低值,冬季（11月-次年2月）北极臭氧快速恢复,这主要是由于南北半球极地地区环流差异和温度差异造成的。南北两极年均O3总量呈下降趋势,两极地区O3总量年际变化最大的季节是春季。近30a,北极在1997和2011年春季（3-4月）分别达到极低值355DU和361DU,但近年来两极臭氧年际变化趋势不明显。2011年春季,北极地区出现的较严重臭氧低值现象从3月中旬至4月中旬持续了近1个月,2010/2011年冬春季平流层低温和臭氧低值对应关系很好。     

Numerical study on the impacts of heterogeneous reactions on ozone formation in the Beijing urban area

The air quality model CMAQ-MADRID （Community Multiscale Air Quality-Model of Aerosol Dynamics, Reaction, Ionization and Dissolution） was employed to simulate summer O3 formation in Beijing China, in order to explore the impacts of four heterogeneous reactions on O3 formation in an urban area. The results showed that the impacts were obvious and exhibited the characteristics of a typical response of a VOC-limited regime in the urban area. For the four heterogeneous reactions considered, the NO2 and HO2 heterogeneous reactions have the most severe impacts on O3 formation. During the O3 formation period, the NO2 heterogeneous reaction increased new radical creation by 30%, raising the atmospheric activity as more NO→NO2 conversion occurred, thus causing the O3 to rise. The increase of O3 peak concentration reached a maximum value of 67 ppb in the urban area. In the morning hours, high NO titration reduced the effect of the photolysis of HONO, which was produced heterogeneously at night in the surface layer. The NO2 heterogeneous reaction in the daytime is likely one of the major reasons causing the O3 increase in the Beijing urban area. The HO2 heterogeneous reaction accelerated radical termination, resulting in a decrease of the radical concentration by 44% at the most. O3 peak concentration decreased by a maximum amount of 24 ppb in the urban area. The simulation results were improved when the heterogeneous reactions were included, with the O3 and HONO model results close to the observations.     

考虑湿度影响的城市气溶胶夜晚温度效应

本文利用一维非定常模式，研究了城市上空干、湿气溶胶粒子对夜间边界层温度的影响。结果表明，湿气溶胶粒子对低层大气有明显的升温作用，而对中上层大气则起降温作用，同时改变了贴地逆温层结构和边界层稳定度。     

Vertical profiles of acetylene in the troposphere and stratosphere

Stratospheric measurements of acetylene up to altitudes of 30 km are presented. The air samples were collected during three different balloon flights, two of them at 44°N, one at 32°N using balloon borne, liquid neon-cooled, cryosamplers. Their acetylene concentration was measured in the laboratory by flame ionisation gaschromatography. The different profiles at 32°N and 44°N are discussed with respect to possible vertical exchange processes and compared with published model calculations.     

The impact of cut-off lows on ozone in the upper troposphere and lower stratosphere over Changchun from ozonesonde observations

In situ measurements of the vertical structure of ozone were made in Changchun(43.53?N, 125.13?E), China, by the Institute of Atmosphere Physics, in the summers of 2010–13. Analysis of the 89 validated ozone profiles shows the variation of ozone concentration in the upper troposphere and lower stratosphere(UTLS) caused by cut-off lows(COLs) over Changchun. During the COL events, an increase of the ozone concentration and a lower height of the tropopause are observed.Backward simulations with a trajectory model show that the ozone-rich airmass brought by the COL is from Siberia. A case study proves that stratosphere–troposphere exchange(STE) occurs in the COL. The ozone-rich air mass transported from the stratosphere to the troposphere first becomes unstable, then loses its high ozone concentration. This process usually happens during the decay stage of COLs. In order to understand the influence of COLs on the ozone in the UTLS, statistical analysis of the ozone profiles within COLs, and other profiles, are employed. The results indicate that the ozone concentrations of the in-COL profiles are significantly higher than those of the other profiles between ±4 km around the tropopause. The COLs induce an increase in UTLS column ozone by 32% on average. Meanwhile, the COLs depress the lapse-rate tropopause(LRT)/dynamical tropopause height by 1.4/1.7 km and cause the atmosphere above the tropopause to be less stable. The influence of COLs is durable because the increased ozone concentration lasts at least one day after the COL has passed over Changchun. Furthermore, the relative coefficient between LRT height and lower stratosphere(LS) column ozone is-0.62,which implies a positive correlation between COL strength and LS ozone concentration.     

夏季南亚高压对其邻近UTLS区域臭氧分布的影响

利用欧洲中期数值预报中心（ECMWF）提供的ERA5高分辨率月平均再分析资料,分析了1991—2020年共30 a夏季6—8月南亚高压对其邻近上对流层—下平流层区域臭氧（O₃）分布的影响。结果表明：ERA5资料能清晰地刻画出南亚高压夏季6—8月的月变化及振荡特征,同时能很好地反映出对应的臭氧低值这一现象。此外,ERA5高分辨率资料还能揭示出臭氧低值的范围和强度变化与南亚高压的范围和强度变化之间存在紧密联系。当南亚高压异常偏强（弱）时,邻近区域的臭氧低值增强（减弱）,当南亚高压中心位置发生振荡时,臭氧浓度纬向偏差的中心也随之发生变化,这种变化在南亚高压偏强年时更明显。但这种联系有一定复杂性,不同月份的相关性存在差异。南亚高压对臭氧浓度的这种影响主要与对流层的空气输送有关,臭氧低值中心位置和范围的变化与位涡低值、位温纬向偏差负值区域分布相对应。