A study of ozone in the Colorado mountains

The seasonal and diurnal variations of ozone mixing ratios have been observed at Niwot Ridge. Colorado. The ozone mixing ratios have been correlated with the NO _x (NO+NO₂) mixing ratios measured concurrently at the site. The seasonal and diurnal variations in O₃ can be reasonably well understood by considering photochemistry and transport. In the winter there is no apparent systematic diurnal variation in the O₃ mixing ratio because there is little diurnal change of transport and a slow photochemistry. In the summer, the O₃ levels at the site are suppressed at night due to the presence of a nocturnal inversion layer that isolated ozone near the surface, where it is destroyed. Ozone is observed to increase in the summer during the day. The increases in ozone correlate with increasing NO _x levels, as well as with the levels of other compounds of anthropogenic origin. We interpret this correlation as in-situ or in-transit photochemical production of ozone from these precursors that are transported to our site. The levels of ozone recorded approach 100 ppbv at NO _x mixing ratios of approximately 3 ppbv. Calculations made using a simple clean tropospheric chemical model are consistent with the NO _x -related trend observed for the daytime ozone mixing ratio. However, the chemistry, which does not include nonmethane hydrocarbon photochemistry, underestimates the observed O₃ production.     

平流层臭氧纬向分布季节变化和行星波的关系

通过分析1992—2001年的HALOE卫星资料,给出了各纬度带平流层的臭氧混合比的纬向分布结构,并分析了其季节变化的特征,同时,利用NCEP/NCAR再分析资料,分析了平流层行星波的结构及其与臭氧纬向分布的关系。结果表明:平流层臭氧混合比的纬向分布季节差异较大,在两半球的夏季平流层臭氧混合比的纬向分布较均匀,其它季节在中高纬的臭氧混合比高值区有一些扰动,并且随着纬度的增大其扰动加强,其中冬季它的扰动最强,这些都与平流层的行星波有相同的特点。对这两种资料进行波谱分析发现,在冬半球臭氧混合比在中高纬的纬向扰动有明显的1波信号,并且与位势高度的1波扰动有相同的位相,因此认为臭氧纬向扰动主要是由行星波引起的,并且在中高纬主要是1波的影响;而低纬地区由于不满足行星波上传的条件,所以臭氧纬向分布不受行星波的影响。分析行星波扰动对臭氧的输送作用也表明,行星波的扰动确实引起臭氧在经向上的输送,从而造成臭氧纬向分布的不对称,并且由于基本气流的输送作用,使得臭氧纬向扰动与行星波造成的原始扰动有一个位相差。     

未来甲烷排放增加对平流层水汽和全球臭氧的影响

利用一个耦合的大气化学-气候模式(WACCM3)研究了地表甲烷排放增加对平流层水汽和全球臭氧变化的影响.结果表明,如果地表甲烷的排放量在2000年的基础上增加50%(达到政府间气候变化专门委员会A1B排放情景中2050年的值),平流层水汽体积分数将平均增加约0.8×10^-6.南半球平流层甲烷转化为水汽的效率比北半球高.在北半球平流层中,1mol甲烷分子可以转化为约1.63mol的水汽分子,而在南半球1mol甲烷分子大概可以转化为约1.82mol的水汽分子.甲烷排放增加50%将使全球中低纬度地区以及北半球高纬度地区的臭氧柱总量增加1%-3%,使南半球高纬度地区臭氧柱总量增加近8%,而秋季(南半球春季)南极地区臭氧柱总量增加幅度可高达20%,南极臭氧的这种显着增加主要是由于甲烷增加造成的化学反馈所致.在北半球中高纬度地区,甲烷增加引起的臭氧变化主要与甲烷氧化导致的水汽增加有关.研究还表明,未来甲烷排放增加对臭氧的恢复作用其实与溴化物排放的减少一样重要.     

The photochemistry of synoptic-scale ozone synthesis: Implications for the global tropospheric ozone budget

The oxidation of nonmethane hydrocarbons represents a source of tropospheric ozone that is primarily confined to the boundary layers of several highly industrialized regions. (Each region has an area greater than one million km²). Using a photochemical model, the global tropospheric ozone budget is reexamined by including the in-situ production from these localized regimes. The results from these calculations suggest that the net source due to this photochemistry, which takes place on the synoptic scale, is approximately as large as the amount calculated for global scale photochemical processes which consider only the oxidation of methane and carbon monoxide. Such a finding may have a considerable impact on our understanding of the tropospheric ozone budget. The model results for ozone show reasonable agreement with the climatological summer distribution of ozone and the oxides of nitrogen at the surface and with the vertical distribution of ozone and nonmethane hydrocarbons obtained during a 1980 field program.     

对流层臭氧影响植被研究进展:观测、参数化方案及应用

对流层臭氧(O_3)作为最重要的大气污染物之一,对植物的形态特征和生理生化指标有着重要影响;并通过作用于陆面植被间接改变全球和区域的碳循环以及气候和环境。本文系统地回顾了对流层臭氧影响陆面植被的观测事实,主要包括其对光合作用、气孔导度、叶面积、生物量、产量等方面的影响;归纳和分析了常用的O_3暴露指数(ozone exposure index)和O_3影响植被的参数化方案的优缺点;并介绍这些参数化方案应用于生态模式和地球系统模式,模拟O_3通过作用于陆面植被对碳、水、能量通量和状态的影响。最后探讨了O_3影响植被在观测、参数化方案及其模拟应用方面亟需解决的问题以及未来发展方向。     

On the transfer of stratospheric ozone into the troposphere near the north pole

A series of nearly daily ozone vertical profiles obtained at station T-3 on Fletcher's Ice Island (85°N, 90°W) during the period January-March 1971 shows several significant ozone intrusions into the troposphere. These intrusions are not only associated with enhanced ozone amounts in the stratosphere but also require tropopause folding events to transport ozone into the troposphere. These folds in the Arctic tropopause appear to be capable of contributing significantly to the ozone budget of the Arctic troposphere during the late winter and spring seasons. The importance of tropopause folding for bringing ozone into the troposphere seen in the daily ozone profiles confirms the results found in the Arctic Gas and Aerosol Sampling Program aircraft flights.     

近50 a平流层强爆发性增温事件及其变化规律分析

按WMO提供的标准，提出了划分强爆发性增温(Sudden Stratospheric Warming，简称SSW)事件的指标，用NCEP／NCAR 30 hPa层逐日温度、高度资料，确定了1950-2002年1-3月期间的35次强SSW事件。在此基础上，给出了强SSW事件发生的气候及异常特征，并从北半球中高纬臭氧及日照年际变化及其年际异常出发，给出了这些特征的部分成因。     

Intercomparison campaign of vertical ozone profiles including electrochemical sondes of ECC and Brewer-Mast type and a ground based UV-differential absorption lidar

An intercomparison campaign was conducted at the Observatoire de Haute Provence (OHP) in Southern France in September 1989 in order to compare the three instruments used for vertical tropospheric ozone profiling in the European TOR (Tropospheric Ozone Research Project) network: balloon borne ECC and Brewer-Mast sondes and a ground based UV-DIAL (DifferentialAbsorptionLidar). Additionally, a stratospheric lidar system and the Dobson spectrophotometer of the OHP were operated. Seven simultaneously measured vertical ozone profiles gave evidence for systematic differences of 15% between both types of electrochemical sondes in the troposphere, the Brewer-Mast sondes reading the smaller ozone values. These differences might be explained on the one hand by a possible contamination of the ozone sensor with reducing substances, causing a negative bias mainly for Brewer-Mast sondes and, on the other hand, by the evolution of the sonde background current during the flight, causing a positive bias for ECC sondes and a negative bias for Brewer-Mast sondes. The tropospheric lidar system, measuring the vertical ozone distribution between 6 and 12–15 km, showed ozone concentrations intermediate between the sonde results. This is in good agreement with its estimated systematic error of better than 7% in the upper troposphere. In the stratosphere, the differences between electrochemical sondes and the lidar are between 5 and 10% before the normalisation with the total ozone values measured by the Dobson spectrophotometer, and always below 5% after. While the Dobson normalisation thus corrects rather well the stratospheric part of the sonde profile, it only partially reduces errors occurring in the troposphere.     

Carbonyl products of the gas phase reaction of ozone with 1,1-disubstituted alkenes

Carbonyl products have been identified and their formation yields measured in experiments involving the gas phase reaction of ozone with 1,1-disubstituted alkenes at ambient T and p=1 atm. of air. Sufficient cyclohexane was added to scavenge the hydroxyl radical in order to minimize OH-alkene and OH-carbonyl reactions. Formation yields (carbonyl formed/ozone reacted) of primary carbonyls were close to the value of 1.0 that is consistent with the mechanism: O₃+R₁R₂C=CH₂ (HCHO+R₁R₂COO)+(1–)(R₁COR₂+H₂COO) where formaldehyde and the ketone R₁ COR₂ are the primary carbonyls and R₁R₂COO and H₂COO are the corresponding biradicals. Measured values of were 0.58–0.82 and indicate modest preferential formation of formaldehyde and the disubstituted biradical as compared to the ketone and the biradical H₂COO. Carbonyls other than the primary carbonyls were identified. Their formation is discussed in terms of subsequent reactions of the disubstituted biradicals R₁R₂COO. Similarities and differences between disubstituted and monosubstituted biradicals are outlined.     

中部型ENSO和平流层准两年振荡对冬季北半球平流层臭氧的联合调制作用

利用观测和再分析资料通过合成分析方法,研究了中部型ENSO和平流层准两年振荡（QBO）对冬季北半球平流层臭氧的独立影响和联合调制作用。研究表明,北半球平流层臭氧在中部型厄尔尼诺年增加,而在中部型拉尼娜年减少;准两年振荡东风位相年份,北半球平流层臭氧增加,准两年振荡西风位相结果则相反。相比之下,北半球中、高纬度平流层臭氧异常对准两年振荡活动的响应明显小于其对ENSO活动的响应。进一步研究发现,准两年振荡东风位相会加强中部型厄尔尼诺事件引起的北半球平流层臭氧的增加,而减弱中部型拉尼娜事件造成的平流层臭氧的减少。在准两年振荡西风位相下,中部型厄尔尼诺事件仅导致北半球平流层臭氧含量少量升高,而中部型拉尼娜事件期间臭氧会大幅度减少。因此,准两年振荡东风位相会加强中部型厄尔尼诺事件对北半球平流层臭氧的影响,而减弱中部型拉尼娜事件对北半球平流层臭氧的影响。准两年振荡西风位相会减弱中部型厄尔尼诺而加强中部型拉尼娜事件对北半球平流层臭氧的影响。      

High atmospheric NO x levels and multiple photochemical steady states

Previous zero-dimensional photochemical calculations indicate that multiple tropospheric steady states may exist, in which different NO _x (NO+NO₂) levels could be supported by the same source of NO _x . To investigate this possibility more closely, a one-dimensional photochemical model has been used to estimate the rate of removal of atmospheric NO _x compounds at different NO _x levels. At low NO _x levels NO _x is photochemically converted to HNO₃, which is removed by either wet or dry deposition. At high NO _x levels formation of HNO₃ is inhibited, and NO _x is removed by a variety of other processes, including rainout of N₂O₄ and N₂O₅, surface deposition of NO and NO₂, and direct dissolution of NO and NO₂ in rainwater. Multiple steady states are possible if surface deposition of NO _x is relatively inefficient. The NO _x source required to trigger high atmospheric NO _x levels is approximately 10 to 15 times the present global emission rate-less than half the source strength predicted by the zero-dimensional model. NO _x mixing ratios in excess of 10^-7 would cause severe damage to the ozone layer and could result in either a climatic warming or cooling, depending upon the amount of NO₂ present.     

The cause of the spring strengthening of the Antarctic polar vortex

The stratospheric polar vortex strengthening from late winter to spring plays a crucial role in polar ozone depletion. The Arctic polar vortex reaches its peak intensity in mid-winter, whereas the Antarctic vortex usually strengthens in early spring. As a result, the strong ozone depletion is observed every year over the Antarctic, while over the Arctic short-term ozone loss occasionally occurs in late winter or early spring. However, the cause of such a difference in the life cycles of the Arctic and Antarctic polar vortices is still not completely clear. Based on the ERA-Interim reanalysis data, we show a high agreement between the seasonal variations of temperature in the subtropical lower stratosphere and zonal wind in the subpolar and polar lower stratosphere in the Southern Hemisphere. Thus, the spring strengthening of the Antarctic polar vortex can occur due to the seasonal temperature increase in the subtropical lower stratosphere in this period.     

近地层臭氧对我国树木生产力和作物产量的影响:进展与展望

大气污染严重威胁了我国陆地生态系统的固碳能力,但随着减污降碳协同治理的快速推进,减缓大气污染将有利于提升陆地碳汇,并切实推动碳达峰碳中和目标的实现。为了更好地理解大气污染与生态系统固碳的关系,本文以主要空气污染物臭氧（O₃）为例,基于田间控制实验的整合分析、剂量响应关系及机理模型三种评估方法综述了近地层O₃污染对植被碳固定影响的最新进展。尽管不同作物种类以及品种、不同功能型木本植物对O₃的响应有着显著的差异,且各种方法的评估结果也不尽相同,但目前O₃浓度造成我国粮食作物减产、森林生产力降低已是不争的事实。持续升高的O₃浓度将严重威胁我国陆地生态系统的固碳能力。利用我国作物和树木的O₃剂量响应方程进行评估的结果表明,在CO₂减排和O₃污染协同治理下,预计2060年我国树木生物量和作物产量将比当前显著提高,增加陆地生态系统碳汇,助力碳中和目标。最后,对如何提高O₃污染环境下植物固碳能力也进行了展望。     

Emission scenarios for a global hydrogen economy and the consequences for global air pollution

Hydrogen is named as possible energy carrier for future energy systems. However, the impact of large-scale hydrogen use on the atmosphere is uncertain. Application of hydrogen in clean fuel cells reduces emissions of air pollutants, but emissions from hydrogen production and leakages of molecular hydrogen could influence atmospheric chemistry. This paper combines a global energy system model and a global atmospheric model to explore the range of impacts of hydrogen on atmospheric chemistry. We found that emissions of molecular hydrogen may range from 0.2 up to 10% (or 25-167 Tg hydrogen/yr) for a global hydrogen energy system. The lower end of this range would in fact be equal to current emissions from fossil fuel combustion. Hydrogen energy use leads to a clear decrease in emissions of carbon monoxide, nitrogen oxides and sulphur dioxide, but large-scale hydrogen production from coal may lead to net increase in emissions of nitrous oxide and volatile organic compound. Compared to a reference scenario, this would lead to positive impacts on surface concentrations of carbon monoxide, nitrogen oxides and ozone. However, if hydrogen leakage would not be minimised it leads to an increase in methane lifetimes and a decrease in stratospheric ozone concentrations.     

Smog Chamber Study on the Ozone Formation Potential of Acetaldehyde

Acetaldehyde is one of the important VOC species of O3 precursors in the atmospheric environment. The influences of relative humidity (RH) and initial VOC/NOx ratio (RCN) on the formation of O3 are studied in smog chamber experiments, and the MCM v3.3.1 mechanism of acetaldehyde is modified based on the experimental results. In low-RH conditions (RH= 11.6％±1.1％), the O3 concentration at 6 h increases first and then decreases with the increase of RCN, and the RCN at the inflection point of O3 concentrations is 3.2. In high-RH experiments (RH = 78.8％±1.0％), variation of the O3 concentration at 6 h with RCN is similar to that in low-RH experiments, but the RCN at the inflection point is 2.8. RH has no significant effect on the O3 concentrations under low RCN (< 3), whereas it has a negative effect under high RCN (> 3). Compared with the experimental results, original MCM v3.3.1 greatly underestimates the O3 concentrations. Addition of both the photolysis process of peroxyacetyl nitrate and the photolysis process of HNO3 on the reactor surface into the original MCM can reduce the difference between the simulated O3 concentrations and the experimental results at 6 h from 24％-35％ and 17％-49％ to 6％-26％ and 10％-42％ under low- and high-RH conditions, respectively. The maximum incremental reactivity (MIR) of acetaldehyde simulated with the modified MCM is 4.0 ppb ppb-1 without considering the effect of other VOCs.     

A model investigation of the impact of increases in anthropogenic NO x emissions between 1967 and 1980 on tropospheric ozone

Recent observations suggest that the abundance of ozone between 2 and 8 km in the Northern Hemisphere mid-latitudes has increased by about 12% during the period from 1970 to 1981. Earlier estimates were somewhat more conservative suggesting increases at the rate of 7% per decade since the start of regular observations in 1967. Previous photochemical model studies have indicated that tropospheric ozone concentrations would increase with increases in emissions of CO, CH₄ and NO _x . This paper presents an analysis of tropospheric ozone which suggests that a significant portion of its increase may be attributed to the increase in global anthropogenic NO _x emissions during this period while the contribution of CH₄ to the increase is quite small. Two statistical models are presented for estimating annual global anthropogenic emissions of NO _x and are used to derive the trend in the emissions for the years 1966–1980. These show steady increase in the emissions during this interval except for brief periods of leveling off after 1973 and 1978. The impact of this increase in emissions on ozone is estimated by calculations with a onedimensional (latitudinal) model which includes coupled tropospheric photochemistry and diffusive meridional transport. Steady-state photochemical calculations with prescribed NO _x emissions appropriate for 1966 and 1980 indicate an ozone increase of 8–11% in the Northern Hemisphere, a result which is compatible with the rise in ozone suggested by the observations.     

A review of global stratospheric aerosol: Measurements, importance, life cycle, and local stratospheric aerosol

Stratospheric aerosol, noted after large volcanic eruptions since at least the late 1800s, were first measured in the late 1950s, with the modern continuous record beginning in the 1970s. Stratospheric aerosol, both volcanic and non-volcanic are sulfuric acid droplets with radii (concentrations) on the order of 0.1–0.5 µm (0.5–0.005 cm^− 3), increasing by factors of 2–4 (10–10³) after large volcanic eruptions. The source of the sulfur for the aerosol is either through direct injection from sulfur-rich volcanic eruptions, or from tropical injection of tropospheric air containing OCS, SO₂, and sulfate particles. The life cycle of non-volcanic stratospheric aerosol, consisting of photo-dissociation and oxidation of sulfur source gases, nucleation/condensation in the tropics, transport pole-ward and downward in the global planetary wave driven tropical pump, leads to a quasi steady state relative maximum in particle number concentration at around 20 km in the mid latitudes. Stratospheric aerosol have significant impacts on the Earth's radiation balance for several years following volcanic eruptions. Away from large eruptions, the direct radiation impact is small and well characterized; however, these particles also may play a role in the nucleation of near tropopause cirrus, and thus indirectly affect radiation. Stratospheric aerosol play a larger role in the chemical, particularly ozone, balance of the stratosphere. In the mid latitudes they interact with both nitrous oxides and chlorine reservoirs, thus indirectly affecting ozone. In the polar regions they provide condensation sites for polar stratospheric clouds which then provide the surfaces necessary to convert inactive to active chlorine leading to polar ozone loss. Until the mid 1990s the modern record has been dominated by three large sulfur-rich eruptions: Fuego (1974), El Chichón (1982) and Pinatubo (1991), thus definitive conclusions concerning the trend of non-volcanic stratospheric aerosol could only recently be made. Although anthropogenic emissions of SO₂ have changed somewhat over the past 30 years, the measurements during volcanically quiescent periods indicate no long term trend in non-volcanic stratospheric aerosol.     

High resolution simulation of recent Arctic and Antarctic stratospheric chemical ozone loss compared to observations

Simulations of polar ozone losses were performed using the three-dimensional high-resolution (1^∘ × 1^∘) chemical transport model MIMOSA-CHIM. Three Arctic winters 1999–2000, 2001–2002, 2002–2003 and three Antarctic winters 2001, 2002, and 2003 were considered for the study. The cumulative ozone loss in the Arctic winter 2002–2003 reached around 35% at 475 K inside the vortex, as compared to more than 60% in 1999–2000. During 1999–2000, denitrification induces a maximum of about 23% extra ozone loss at 475 K as compared to 17% in 2002–2003. Unlike these two colder Arctic winters, the 2001–2002 Arctic was warmer and did not experience much ozone loss. Sensitivity tests showed that the chosen resolution of 1^∘ × 1^∘ provides a better evaluation of ozone loss at the edge of the polar vortex in high solar zenith angle conditions. The simulation results for ozone, ClO, HNO₃, N₂O, and NO _y for winters 1999–2000 and 2002–2003 were compared with measurements on board ER-2 and Geophysica aircraft respectively. Sensitivity tests showed that increasing heating rates calculated by the model by 50% and doubling the PSC (Polar Stratospheric Clouds) particle density (from 5 × 10⁻³ to 10⁻² cm⁻³) refines the agreement with in situ ozone, N₂O and NO _y levels. In this configuration, simulated ClO levels are increased and are in better agreement with observations in January but are overestimated by about 20% in March. The use of the Burkholder et al. (1990) Cl₂O₂ absorption cross-sections slightly increases further ClO levels especially in high solar zenith angle conditions. Comparisons of the modelled ozone values with ozonesonde measurement in the Antarctic winter 2003 and with Polar Ozone and Aerosol Measurement III (POAM III) measurements in the Antarctic winters 2001 and 2002, shows that the simulations underestimate the ozone loss rate at the end of the ozone destruction period. A slightly better agreement is obtained with the use of Burkholder et al. (1990) Cl₂O₂ absorption cross-sections.     

Influence of Atmospheric Particulate Matter on Ozone in Nanjing,China:Observational Study and Mechanistic Analysis

Particulate matter with diameters of 2.5 μm or smaller(PM_(2.5)) and ozone(O_3) are major pollutants in the urban atmosphere. PM_(2.5) can affect O_3 by altering the photolysis rate and heterogeneous reactions. However, these two processes and their relative importance remain uncertain. In this paper, with Nanjing in China as the target city, we investigate the characteristics and mechanism of interactions between particles and O_3 based on ground observations and numerical modeling.In 2008, the average concentrations of PM_(2.5) and O_3 at Caochangmen station are 64.6 ± 47.4 μg m~(-3) and 24.6 ± 22.8 ppb,respectively, while at Pukou station they are 94.1 ± 63.4 μg m~(-3) and 16.9 ± 14.9 ppb. The correlation coefficient between PM_(2.5) and O_3 is -0.46. In order to understand the reaction between PM_(2.5) and O_3, we construct a box model, in which an aerosol optical property model, ultraviolet radiation model, gas phase chemistry model, and heterogeneous chemistry model,are coupled. The model is employed to investigate the relative contribution of the aforementioned two processes, which vary under different particle concentrations, scattering capability and VOCs/NOxratios(VOCs: volatile organic compounds;NOx: nitric oxide and nitrogen dioxide). Generally, photolysis rate effect can cause a greater O_3 reduction when the particle concentrations are higher, while heterogeneous reactions dominate O_3 reduction with low-level particle concentrations.Moreover, in typical VOC-sensitive regions, O_3 can even be increased by heterogeneous reactions. In Nanjing, both processes lead to O_3 reduction, and photolysis rate effect is dominant. Our study underscores the importance of photolysis rate effect and heterogeneous reactions for O_3, and such interaction processes should be fully considered in future atmospheric chemistry modeling.     

Determination of Dominant Pathways in Chemical Reaction Systems: An Algorithm and Its Application to Stratospheric Chemistry

The analysis of complex chemical reaction systems is frequently complicatedbecause of the coexistence of fast cyclic reaction sequences and slower pathways that yield a net production or destruction of a certain species of interest.An algorithm for the determination of both these types of reaction sequences (in a given reaction system) is presented. Under the assumption that reaction rates are known, it finds the mostimportant pathways by solving a linear optimization problem for each of them.This algorithm may be used as a tool for the interpretation of chemical model runs.For illustration, it is applied to examples in stratospheric chemistry, including the determination of catalytic ozone destruction cycles.