Responses of the tropospheric ozone and odd hydrogen radicals to column ozone change

The response of tropospheric ozone to a change in solar UV penetration due to perturbation on column ozone depends critically on the tropospheric NO _x (NO+NO₂) concentration. At high NO _x or a polluted area where there is net ozone production, a decrease in column ozone will increase the solar UV penetration to the troposphere and thus increase the tropospheric ozone concentration. However, the opposite will occur, for example, at a remote oceanic area where NO _x is so low that there is net ozone destruction. This finding may have important implication on the interpretation of the long term trend of tropospheric ozone. A change in column ozone will also induce change in tropospheric OH, HO₂, and H₂O₂ concentrations which are major oxidants in the troposphere. Thus, the oxidation capacity and, in turn, the abundances of many reduced gases will be perturbed. Our model calculations show that the change in OH, HO₂, and H₂O₂ concentrations are essentially independent of the NO _x concentration.     

Ozone in ambient air at a tropical megacity, Delhi: characteristics, trends and cumulative ozone exposure indices

Seven year data of hourly surface ozone concentration is analyzed to study diurnal cycle, trends, excess of ozone levels above threshold value and cumulative ozone exposure indices at a tropical megacity, Delhi. The ozone levels clearly exhibit a diurnal cycle, similar to what has been found in other urban places. A sharp increase in the ozone levels during forenoon and a sharp decrease in the early afternoon can be observed. The average rate of increase in ozone concentration between 09 and 12 h has been observed to be 7.1 ppb h⁻¹. We find that the daily maximum and daytime 8-h (10–17 h) ozone levels are increasing at a rate of about 1.7 (± 0.7) and 1.3 (± 0.56) ppb y⁻¹, respectively. The directives on ozone pollution in ambient air provided by United Nations Economic Commission for Europe and World Health Organization for vegetation (AOT40) and human health protection were used to assess the air quality. The present surface ozone levels in the city are high enough to exceed “Critical Levels” which are considered to be safe for human health, vegetation and forest. The human health threshold was exceeded for up to ~45 days per year. The AOT40 (Accumulated exposure Over a Threshold of 40 ppb) threshold was exceeded significantly during winter (D-J-F) and pre-monsoon (M-A-M) (Rabi crop growing season) season in India. Translating AOT40 exceedances during pre-monsoon into relative yield loss we estimate yield loss of 22.7%, 22.5%, 16.3% and 5.5% for wheat, cotton, soybean and rice, respectively.     

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.     

Performance Evaluation of a Self-Developed Ozonesonde and Its Application in an Intensive Observational Campaign

To make a detailed test on the reliability and detection performance of the electrochemical concentra- tion cell （ECC） type ozonesonde which had been devel- oped and preliminarily evaluated by the authors, an inten- sive ozonesonde release experiment was held at two sites in Beijing and Changchun in June 2013. The results showed that the mean background current and its standard deviation were 0.03 （0.04） pA and 0.02 （0.03） pA in Bei- jing （Changchun）. The average response time and its standard deviation were 27.8 s （30.4 s） and 4.0 s （3.7 s） in Beijing （Changchun）. The ozone partial pressure profiles at both sites showed a central peak in the stratosphere and a side peak in the boundary layer. Large variation in ozone partial pressure was observed at the middle levels of the atmosphere （10-17 kin）. A more marked gradient of ozone change was observed in Beijing （3.4 mPa km-1） at the lower atmosphere level, as compared to that in Changchun （0.4 mPa km-l）. The results presented in this paper indicate that this self-developed ozonesonde shows a high level of reliability and good performance. The ozonsonde is expected to play an important role in opera- tional observations of ozone profiles.     

A modeling study of effective radiative forcing and climate response due to tropospheric ozone

This study simulates the effective radiative forcing(ERF) of tropospheric ozone from 1850 to 2013 and its effects on global climate using an aerosol–climate coupled model, BCC AGCM2.0.1 CUACE/Aero, in combination with OMI(Ozone Monitoring Instrument) satellite ozone data. According to the OMI observations, the global annual mean tropospheric column ozone(TCO) was 33.9 DU in 2013, and the largest TCO was distributed in the belts between 30°N and 45°N and at approximately 30°S; the annual mean TCO was higher in the Northern Hemisphere than that in the Southern Hemisphere;and in boreal summer and autumn, the global mean TCO was higher than in winter and spring. The simulated ERF due to the change in tropospheric ozone concentration from 1850 to 2013 was 0.46 W m~(-2), thereby causing an increase in the global annual mean surface temperature by 0.36℃, and precipitation by 0.02 mm d~(-1)(the increase of surface temperature had a significance level above 95%). The surface temperature was increased more obviously over the high latitudes in both hemispheres, with the maximum exceeding 1.4?C in Siberia. There were opposite changes in precipitation near the equator,with an increase of 0.5 mm d~(-1)near the Hawaiian Islands and a decrease of about-0.6 mm d~(-1)near the middle of the Indian Ocean.     

Subsonic aircraft and ozone trends

Growth in subsonic air traffic over the past 20 years has been dramatic, with an annual increase of }6.1% over the decade between 1978 and 1988. Furthermore, aircraft activities in the year 2000 are predicted to be double those of 1990, with a shift towards more high-flying, longhaul subsonics. Aircraft exhaust gases increase the amount of nitrogen oxides (NO _x ) in the upper troposphere/lower stratosphere through injection at cruise altitudes. Given that NO _x is instrumental in tropospheric ozone production and stratospheric ozone destruction, it is important to determine the influence of subsonic aircraft NO _x emissions on levels of atmospheric ozone. This paper describes calculations designed to investigate the impact that subsonic aircraft may already have had on the atmosphere during the 1980s, run in a 2-D chemical-radiative-transport model. The results indicate a significant increase in upper tropospheric ozone over the decade arising from aircraft emissions. However, when comparing model results with observational data, certain discrepancies appear. Lower stratospheric ozone loss over the 1980s does not appear to be greatly altered by the inclusion of aircraft emissions in the model. However, given the trend in greater numbers of long-haul subsonic aircraft, this factor must be considered in any further calculations.     

Signatures of a Universal Spectrum for Nonlinear Variability in Daily Columnar Total Ozone Content

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Long-term measurements of surface ozone in the German Democratic Republic

The ozone concentration near the earth's surface has been measured at some stations in the GDR for more than 30 yr using the wet chemical method. Even at rural stations the ozone data show a significant linear increase by about 1–3% yr^–1. The ozone increase being stronger in summer than in winter is assumed to be due to photochemical ozone production from increasing anthropogenic emissions of trace gases that are transported over long distances. A weaker ozone increase by only about 0.2% per year was observed in the free troposphere (5.5 km) from balloon-soundings at Lindenberg within the period 1975–1984. If the ozone trends continue, the ozone concentration near the surface and its seasonal amplitude will have doubled around the turn of the century as compared to the mid-fifties.     

Model analysis of seasonal variations in tropospheric ozone and carbon monoxide over East Asia

Temporal-spatial variations in tropospheric ozone concentrations over East Asia in the period from 1 January 2000 to 31 December 2004 were simulated by using the Models-3 Community Multi-scale Air Quality (CMAQ) modeling system with meteorological fields calculated by the Regional Atmospheric Modeling System (RAMS). The simulated concentrations of ozone and carbon monoxide were compared with ground level observations at two remote sites, Ryori (39.03°N, 141.82°E) and Yonagunijima (24.47°N, 123.02°E). The co...     

The possible influences of the increasing anthropogenic emissions in India on tropospheric ozone and OH

A 3-D chemical transport model (OSLO CTM2) is used to investigate the influences of the increasing anthropogenic emission in India. The model is capable of reproducing the observational results of the INDOEX experiment and the measurements in summer over India well. The model results show that when NOx and CO emissions in India are doubled, ozone concentration increases, and global average OH decreases a little. Under the effects of the Indian summer monsoon, NOx and CO in India are efficiently transported into the middle and upper troposphere by the upward current and the convective activities so that the NOx, CO, and ozone in the middle and upper troposphere significantly increase with the increasing NOx and CO emissions. These increases extensively influence a part of Asia, Africa, and Europe, and persist from June to September.     

Temporal variations in surface ozone and its precursors and meteorological effects at an urban site in China

Continuous measurements of ozone and its precursors including NO, NO₂, and CO at an urban site (32°03′N, 118°44′E) in Nanjing, China during the period from January 2000 to February 2003 are presented. The effects of local meteorological conditions and distant transports associated with seasonal changed Asian monsoons on the temporal variations of O₃ and its precursors are studied by statistical, backward trajectory, and episode analyses. The diurnal variation in O₃ shows high concentrations during daytime and low concentrations during late night and early morning, while the precursors show high concentrations during night and early morning and low concentrations during daytime. The diurnal variations in air pollutants are closely related to those in local meteorological conditions. Both temperature and wind speed have significant positive correlations with O₃ and significant negative correlations with the precursors. Relative humidity has a significant negative correlation with O₃ and significant positive correlations with the precursors. The seasonal variation in O₃ shows low concentrations in late autumn and winter and high concentrations in late spring and early summer, while the precursors show high concentrations in late autumn and winter and low concentrations in summer. Local mobile and stationary sources make a great contribution to the precursors, but distant transports also play a very important role in the seasonal variations of the air pollutants. The distant transport associated with the southeastern maritime monsoon contributes substantially to the O₃ because the originally clean maritime air mass is polluted when passing over the highly industrialized and urbanized areas in the Yangtze River Delta. The high frequency of this type of air mass in summer causes the fact that a common seasonal characteristic of surface O₃ in East Asia, summer minimum, is not observed at this site. The distant transports associated with the northern continental monsoons that dominate in autumn and winter are related to the high concentrations of the precursors in these two seasons. This study can contribute to a better understanding of the O₃ pollution in vast inland of China affected by meteorological conditions and the rapid urbanization and industrialization.     

青藏高原春季不同地区臭氧和大气温度变化趋势的差异性

利用1979—2018年太阳后向散射紫外辐射计SBUV(/2)星下点臭氧遥感资料,结合ERA-Interim和MERRA-2大气温度再分析资料,考察青藏高原区域内拉萨和共和两地春季臭氧和大气温度变化趋势的差异性。结果表明拉萨和共和两个地区的臭氧和大气温度逆转趋势均发生于1999年。对比2008年以来青藏高原整体臭氧总量变化速率（4.5 DU/(10 a)),拉萨臭氧总量变化更快,为5.9 DU/(10 a),共和相对较慢,仅为3.7 DU/(10 a);同时,1999年以来拉萨和共和春季下平流层（100~30 hPa）大气温度分别以0.5~1.4℃/(10 a)和0.01~0.9℃/(10 a)速率增加,上对流层(250~175 hPa)大气温度分别以0.2~1.5℃/(10 a)和0.2~1.2℃/(10 a)速率降低。与2008年以来高原整体大气温度变化相比较,均慢于高原下平流层（125~70 hPa) 1~2℃/(10 a)的增温速率,快于高原上对流层（225~175 hPa）0.4~1.1℃/(10 a)的降温速率。两地臭氧与大气温度的相关系数和回归系数计算结果表明,拉萨和共和两个地区1999年以来春季臭氧恢复速率的不同是导致两地同期下平流层-上对流层温度逆转速率差异的重要因子之一。     

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.     

2008年以来青藏高原春季大气温度逆转趋势及其与臭氧总量变化之间的可能联系

利用ERA-Interim和MERRA-2再分析资料,考察1980—2017年青藏高原大气温度变化趋势和规律,年、季、月不同时间尺度分析结果均揭示2008年以来青藏高原春季大气温度变化呈现逆转趋势：高原上空平流层下部150~50 hPa呈现明显的增温趋势（1.0~2.7℃/10a),对流层上部300~175 hPa呈现明显的降温趋势（-3.1~-1.0℃/10a),这与此前的大气温度变化趋势完全相反。利用TOMS和OMI卫星臭氧遥感资料,考察同期青藏高原臭氧总量变化特征,表明2008年以来青藏高原臭氧总量也表现出逆转的增加趋势,与大气温度逆转趋势吻合,从冬末至春季各月均有显著增加趋势,尤以5月臭氧总量增加速率最大,达13.7 DU/10a。青藏高原春季大气温度变化趋势与同期臭氧总量变化特征紧密相关,2008年后臭氧总量的快速恢复可能是引起大气温度逆转趋势的一个重要影响因素。     

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.     

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.     

Relative roles of dynamic and thermodynamic processes in causing positive and negative global mean SST trends during the past 100 years

Global mean surface temperature (GMST) during 1910–2012 experienced four alternated rapid warming and warming hiatus phases. Such a temporal variation is primarily determined by global mean sea surface temperature (SST) component. The relative roles of ocean dynamic and thermodynamic processes in causing such global mean SST variations are investigated, using two methods. The first method is ocean mixed layer heat budget analysis. The budget diagnosis result shows that the thermodynamic processes dominate in the rapid warming phases, while the ocean dynamics dominate during the hiatus phases. The second method relies on the diagnosis of a simple equilibrium state model. This model captures well the horizontal distribution of SST difference between two warmer and cooler equilibrium states during either the rapid warming or hiatus phases. It is found that the SST difference during the rapid warming phases is primarily controlled by the increase of downward longwave radiation as both column integrated water vapor and CO₂ increase during the phases. During the hiatus phases, the water vapor induced greenhouse effect offsets the CO₂ effect, and the SST cooling tendency is primarily determined by the ocean dynamics over the Southern Ocean and tropical Pacific. The SST pattern associated with the Interdecadal Pacific Oscillation (IPO) might be responsible for the remote and local ocean dynamic responses through induced wind change.     

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.     

重庆市臭氧污染及其气象因子预报方法对比研究

利用2014年1月1日至2018年12月31日的重庆市空气质量日均值资料,分析了重庆近5 a臭氧污染的特征。发现重庆市臭氧是除PM_2.5以外的第二大大气污染物,具有较强的季节变化特征,主要污染时段位于夏半年,在7—8月臭氧污染程度明显超过了PM_2.5。臭氧年平均浓度呈现逐年增加的趋势,首要污染物为臭氧的日数在2018年首次超过PM_2.5,臭氧成为2018年重庆市的第一大污染物,表明重庆正在由一个以颗粒物污染为主的城市转变为臭氧污染为主的城市。通过对同期逐日气象资料与臭氧8 h滑动平均日最大值相关性分析发现,大气温度、湿度及气压均为影响臭氧污染的重要气象因子。利用气象影响因子,采用逐步回归、支持向量机、神经网络方法对臭氧8 h滑动平均日最大值进行预报实验表明,三种预报模型均具有较强的预报能力,但总体来看预报均比实况略偏小。支持向量机方法的预报效果要稍好于逐步回归和神经网络方法,可为重庆市臭氧浓度预报提供参考。     

A photoelectric detector for the measurement of photolysis frequencies of ozone and other atmospheric molecules

Photoelectric detectors for the measurement of photolysis frequencies of different trace gases in the atmosphere are described. They exhibit uniform response characteristics over one hemisphere (2 sr) and wavelength characteristics closely matched to those of the photolysis frequencies J _O1D, J _NO2, and J _NO3, respectively. Absolute calibration of the J _O1D detector was performed by chemical actinometry with an accuracy of ±16 percent. Simultaneous measurements of J _NO2 and J _O1D are presented.