长三角地区典型城市臭氧及其前体物时空分布特征

基于美国宇航局NASA/AURA卫星臭氧监测仪OMI数据,分析了2005—2014年长三角地区及其典型城市对流层O_3、NO_2柱浓度和HCHO大气总柱浓度的时空分布特征。结果表明:10 a间,长三角地区对流层O_3柱浓度和HCHO总柱浓度呈现增长趋势,O_3增量为0.23ppbv/10 a,HCHO增量为0.07×10~(16) mol/(cm~2·10 a),对流层NO_2柱浓度呈现降低趋势,减量为0.06×10~(15)mol/(cm~2·10 a);长三角地区对流层O_3柱浓度最大值出现在3、4、5月,而对流层NO_2柱浓度最大值出现在1、12月,HCHO总柱浓度最大值出现在6、7月;对流层O_3柱浓度的高值区分布在长三角中部、北部区域,对流层NO_2柱浓度高值区分布于长三角中部,HCHO总柱浓度高值区相对分散,且四季的分布各不相同。O_3与NO_2和HCHO在时间和空间上呈现一定的相关性。     

临安冬夏季SO2、NO2和O3体积分数特征及与气象条件的关系

对临安大气本底站2003-2004年冬、夏季二氧化氮(NO2)、二氧化硫(SO2)、臭氧(O3)进行了分析.结果表明:冬季NO2和SO2平均体积分数分别为19.48×10-9和35.74 x10-9,而夏季的平均体积分数分别为4.81×10-9和8.12×10-9,冬季高于夏季;O3在夏季的平均体积分数为33.55×10-9,略高于冬季的25.44×10-9;夜间NO2和SO2体积分数比白天高,并且NO2呈明显的单峰单谷型分布,O3也呈单峰型但峰值出现在白天.NO2、SO2体积分数存在着明显的“假日效应”,假日比非假日低,周五高于假日和非假日;但O3体积分数没有明显的假日效应.降水对SO2有明显的清除作用,但对NO2的清除作用不明显.与风向对比发现,夏季高体积分数的NO2、SO2都受到NW、WNW风的影响,冬季则分别受NE和SW、SSW风的影响;而O3受风向的影响较复杂,与局地光化学反应有关.     

南极长城站大气臭氧和NO2的观测研究

在中国第五次南极考察社长城站的科学研究活动中,开展了与南极臭氧洞有关的大气臭氧和NO_2柱含量的观测。观测采用地面吸收光谱的原理进行。从1988年12月到1989年2月的观测结果表明,长城站区臭氧柱含量平均值为341DU,与常年平均结果相当。NO_2的平均柱含量为2.16×10~(18)cm~(-2)。无论是臭氧或NO_2的柱含量都有明显的日变化。     

Satellite Measurements of Tropospheric Column O<Subscript>3</Subscript> and NO<Subscript>2</Subscript> in Eastern and Southeastern Asia: Comparison with a Global Model (MOZART-2)

Satellite measurements of tropospheric column O₃ and NO₂ in eastern and southeastern Asia are analyzed to study the spatial and seasonal characteristics of pollution in these regions. Tropospheric column O₃ is derived from differential measurements of total column ozone from Total Ozone Mapping Spectrometer (TOMS), and stratospheric column ozone from the Microwave Limb Sounder (MLS) instrument on the Upper Atmosphere Research Satellite (UARS). The tropospheric column NO₂ is measured by Global Ozone Monitoring Experiment (GOME). A global chemical and transport model (Model of Ozone and Related Chemical Tracers, version 2; MOZART-2) is applied to analyze and interpret the satellite measurements. The study, which is based on spring, summer, and fall months of 1997 shows generally good agreement between the model and satellite data with respect to seasonal and spatial characteristics of O₃ and NO₂ fields. The analysis of the model results show that the industrial emission of NO_x (NO + NO₂) contributes about 50%–80% to tropospheric column NO₂ in eastern Asia and about 20%–50% in southeastern Asia. The contribution of industrial emission of NO_x to tropospheric column O₃ ranges from 10% to 30% in eastern Asia. Biomass burning and lightning NO_x emissions have a small effect on tropospheric O₃ in central and eastern Asia, but they have a significant impact in southeastern Asia. The varying effects of NO_x on tropospheric column ozone are attributed to differences in relative abundance of volatile organic compounds (VOCs) with respect to total nitrogen in the two regions.     

Sampling of Chemical Constituents in Electrically Active Convective Systems: Results and Cautions

On flights of a P3-B turboprop and a WB-57F jet aircraft within thunderstorm systems, short term spikes (1–2 sec or less in duration) in NO and O₃ were recorded and are attributed to hot or cold discharges occurring on the aircraft fuselage or air sampling inlets. One such spike of only ∼300 msec duration reached 325 ppbv of NO on the flight of the jet aircraft while at 13.8 km altitude. In a lightning flash to the P3-B aircraft, production of NO (expected) and NO₂ (unexpected) were directly observed. The NO production was ∼ 1.7 x 10²² molecules/m of flash length. In the P3-B flight at 5.5 km altitude and over a distance of ∼ 275 km within a highly electrically active thunderstorm complex in the equatorial central Pacific Ocean, there was no evidence of production of O₃ or CO by lightning flashes or by any type of hot or cold discharge involved in the development of free-air lightning flashes.     

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.     

NUMERICAL SIMULATION OF THE SEASONAL VARIATION OF TROPOSPHERIC OZONE OVER CHINA

An updated version of the Regional Acid Deposition Model(RADM)driven by meteorologicalfields derived from Chinese Regional Climate Model(CRegCM)is used to simulate seasonal variationof tropospheric ozone over the eastern China.The results show that:(1)Peak O_3 concentration moves from south China to north China responding to the changing ofsolar perpendicular incidence point from south to north.When solar perpendicular incidence pointmoves from north to south,so does the peak O_3 concentration.(2)In the eastern China.the highest O_3 month-average concentration appears in July.thelowest in January and the medium in April and October.The pattern mainly depends on the solarradiation,the concentration of O_3 precursors NO_x and NMHC and the ratio of NMHC/NO_x.(3)Daily variations of O_3 over the eastern China are clear.Namely,O_3 concentrations rise withthe sun rising and the maximums appear at noon.then O_3 concentrations decrease.The highest dailyvariation range of O_3 appears in summer(40×10~(-9) in volume fraction)and the lowest in winter(20×10~(-9) in volume fraction).(4)Daily variations of O_3 over the western China are not clear.The daily variation range of O_3 isless than 10×10~(-9) in volume fraction.     

NO2 total column evolution during the 1989 spring at Antarctica Peninsula

Ground-based visible differential absorption spectrometry during twilight has been used for NO₂ total column observations at the Antarctica Peninsula, Marambio Base (64S, 56W), during the austral spring of 1989 (9 September to 25 November).Results show moderate NO₂ vertical column levels of 1.5 to 2.5×10¹⁵ molec cm^-2 in the morning and 2 to 3×10¹⁵ molec cm^-2 in the evening until middle October, highly modulated by planetary wave activity. From that date until the end of the period, a steady increase occurs which is associated with the rising of lower stratosphere temperature as the vortex weakens, reaching values of 5×10¹⁵ molec cm^-2 in late November, with small a.m.-p.m. differences. NO₂ is found to be positively correlated to both total ozone and 50 hPa temperature during the entire spring. However, when analyzing the departures from linear trends, a highly negative correlation has been observed from day 301 onwards.     

Behaviour,of stratospheric NO2 during stratospheric warming of January‐February 1979

Abstract

Ground‐based measurements of stratospheric NO₂, using absorption spectroscopy of twilight sky in the spectral region 437–451 nm, have been made at Calgary (51.08°N, 114.13°W), Alberta, Canada, during the period December 1978‐March 10, 1979. The NO₂ showed a rather steady behaviour in the month of December when there was no stratospheric warming in progress; the monthly average of the afternoon vertical column abundance for December was 1.7 × 10¹⁵ cm². In the rest of the observation period the NO₂ showed a complex behaviour, but this behaviour appears to be explicable in terms of the stratospheric circulation changes taking place in that period due to the occurrence of a stratospheric warming event.     

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.     

北京地区的闪电时空分布特征及不同强度雷暴的贡献

利用北京闪电定位网(BLNET,Beijing Lightning Network)和SAFIR3000(Surveillance et Alerte Foudre par Interometrie Radioelectrique)定位网7年共423次雷暴的闪电资料,并按照雷暴产生闪电多少,同时参考雷达回波和雷暴持续时间,将雷暴划分为弱雷暴(≤1000次)、强雷暴(>1000次且≤10000次)和超强雷暴(>10000次),分析了北京地区的闪电时空分布特征及不同强度等级雷暴对闪电分布的贡献。北京总闪电密度最大值约为15.4 flashes km-2a(^-1),平均值约为1.9 flashes km^-2a(^-1),大于8 flashes km^-2a(^-1)的闪电密度高值区基本分布在海拔高度200 m等高线以下的平原地带。不同强度雷暴对总雷暴闪电总量贡献不同,弱雷暴(超强雷暴)次数多(少),产生的闪电少(多),超强雷暴和强雷暴产生的闪电分别占总雷暴闪电的37%和56%。不同强度雷暴对总雷暴的闪电密度高值中心分布和闪电日变化特征影响显著,昌平区东部、顺义区中东部和北京主城区是总雷暴闪电密度大于12 flashes km-2a(-1)的三个主要高值区中心,前两个高值中心受强雷暴影响大,而主城区高值中心主要受超强雷暴影响。总雷暴晚上频繁的闪电活动主要受超强雷暴和强雷暴影响,这两类雷暴晚上闪电活动活跃,分别占各自总闪电的69%和65%,而弱雷暴闪电活动白天陡增很快,对总雷暴午后的闪电活动影响大。另外,不同下垫面条件闪电日变化差异大,山区最强的闪电活动出现在白天,午后闪电活动增强很快,主峰值出现在北京时间18:00,而平原最强的闪电活动发生在晚上,平原(山麓)的主峰值比山区推迟了约1.5小时(1小时)。     

Lower/middle tropospheric ozone variability in Senegal during pre-monsoon and monsoon periods of summer 2008: observations and model results

During the summer (8 June through 3 September) of 2008, 9 ozone profiles are examined from Dakar, Senegal (14.75°N, 17.49°W) to investigate ozone (O₃) variability in the lower/middle troposphere during the pre-monsoon and monsoon periods. Results during June 2008 (pre-monsoon period) show a reduction in O₃ concentrations, especially in the 850–700 hPa layer with Saharan Air Layer (SAL) events. However, O₃ concentrations are increased in the 950–900 hPa layer where the peak of the inversion is found and presumably the highest dust concentrations. We also use the WRF-CHEM model to gain greater insights for observations of reduced O₃ concentrations during the monsoon periods. In the transition period between 26 June and 2 July in the lower troposphere (925–600 hPa), a significant increase in O₃ concentrations (10–20 ppb) occur which we suggest is caused by enhanced biogenic NO_X emissions from Sahelian soils following rain events on 28 June and 1 July. The results suggest that during the pre-monsoon period ozone concentrations in the lower troposphere are controlled by the SAL, reducing ozone concentrations through heterogeneous chemical processes. At the base of the SAL we also find elevated levels of ozone, which we attribute to biogenic sources of NO_X from Saharan dust that are released in the presence of moist conditions. Once the monsoon period commences, lower ozone concentrations are observed and modeled which we attribute to the dry deposition of ozone and episodes of ozone poor air that is horizontally transported into the Sahel from low latitudes by African Easterly Waves (AEWs).     

Nitrogen dioxide column content measurements made from an aircraft between 5° and 82°N

In the first two weeks of May 1981, the research jet of the German Aerospace Research Establishment (DFVLR) was charted to fly a meridional section between 5° and 82°N. A scanning filter photometer, developed at the Max Planck Institut für Aeronomie to measure column content values of atmospheric ozone and nitrogen dioxide, using ultra violet and visible absorption techniques, constituted part of the experimental payload for this campaign that was called SIMOC. The vertical NO₂ column content above the aircraft, flying at approximately 10 km, was found to decrease rapidly from 6.9×10¹⁵ molecules cm^-2 to 2.5×10¹⁵ molecules cm^-2 around 50°N and then to increase again north of 75°N. A sharp rise in the NO₂ content was observed south of the subtropical jet but this could possibly be due to the increased depth of the troposphere above the aircraft in these regions.     

武汉市2018年4—9月臭氧及其前体物非线性关系研究

近年来武汉市臭氧污染日益严峻,成为影响空气质量达标的瓶颈,弄清臭氧及其前体物非线性关系是臭氧防控的关键和基础.本研究基于武汉中心城区2018年4—9月臭氧及其前体物在线观测数据,分析出武汉市臭氧浓度受前体物和气象条件等因素的共同影响,呈较为明显的季节变化和日变化特征.观测期间武汉市大气挥发性有机物（VOCs）平均体积分数为32.5×10^-9,烷烃是武汉市VOCs的主要组分,其次是含氧VOCs （OVOCs）和卤代烃.利用基于观测的模型定量分析臭氧与前体物之间的关系,发现削减VOCs会引起臭氧生成潜势的显著下降,而削减氮氧化物则会使臭氧生成潜势升高,说明武汉市臭氧生成处于VOCs控制区.在人为源VOCs中,间/对二甲苯和邻二甲苯的相对增量反应活性（RIR）最高,是影响臭氧生成的关键组分.     

Studying air pollution with kitt peak solar flux atlas — analysis method and results of observation

For the measurement of atmospheric NO2 vertical column density (VCD), Kitt Peak Solar Flux Atlas can be substituted as an extraterrestrial solar radiation. Compared with differential analysis method, the Taylor expansion of integrated transfer equation underestimates the VCD. This underestimation is as large as 35% when the amount of NO2 is 1 × 1017 cm－2 and observation is conducted with an air mass factor of 10. Even when the VCD is 2 × 1016 cm－2 and the air mass factor is 4, the relative error of the retrieved VCD is still no less than 3%. If the observation is restricted under the small air mass factor condition (≤4), with Kitt Peak Solar spectrum as an extraterrestrial solar radiation, only an atmospheric layer of 2 km thick from ground can be studied, which will make the absorption too weak to be detected by normal instruments.The VCD in winter Tokyo area was observed and analyzed by differential method, which shows a good precision even when the absorption is as low as 3%. The largest average VCD was about 1.3 × 1017 cm－2, and the lowest was about 1.3 × 1016 cm－2. The trend of its variation was almost the same as the ground level observation by Saltzman reagent method.     

Observation of Filterable Bromine Variabilities During Arctic Tropospheric Ozone Depletion Events in High (1hour) Time Resolution

The halogen ions Br^- and Cl^- together with NO₃ ^-, SO₄ ⁼, MSA^- (methane sulfonate), Na⁺ and NH₄ ⁺ were analysed by ion chromatography in extracts of more than 800 aerosol cellulose filter samples taken at Ny Ålesund, Svalbard (79°N, 12°E) in spring 1996 (March 27 - May 16) within the European Union project ARCTOC (Arctic Tropospheric Ozone Chemistry). Anticorrelated variations between f-Br (filterable bromine, i.e. water soluble bromine species that can be collected by aerosol filters) and ozone within the arctic troposphere were evaluated at a resolution of 1 or 2 hours for periods with depleted ozone and 4 hours at normal ozone. A mean f-Br concentration of 11 ng m^-3 (0.14 nmol m^-3) was observed for the whole campaign, while maximum concentrations of 80 ng m^-3 (1 nmol m^-3) were detected during two total O₃-depletion events (O₃ drop to mixing ratios below the detection limit of < 2 ppb). Anticorrelation between f-Br and O₃ was also seen during minor O₃-depletion episodes (sudden drop in O₃ by at least 10 ppb, but O₃ still exceeding the detection limit) and even for ozone variations near its background level (40-50 ppb). A time lag of about 10 hours between the change of ozone and of f-Br concentrations could only be found during a total ozone depletion event, when f-Br reached its maximum values several hours after ozone was totally destroyed. Bromine oxide (BrO) concentrations, measured by DOAS (Differential Optical Absorption Spectroscopy), and f-Br showed a coincident variability during almost the entire campaign (except in the case of total O₃-loss). Frequently enhanced anthropogenic nitrate and sulphate concentrations were observed during O₃-depletion periods. At O₃ concentrations < 10 ppb sulphate and nitrate exceed their typical mean level by 54% and 77%, respectively. This may indicate a possible connection between acidity and halogen release.     

Study of Ozone and NO2 over Gadanki – a rural site in South India

We have studied long-term changes in tropospheric NO₂ over South India using ground-based observations, and GOME and OMI satellite data. We have found that unlike urban regions, the region between Eastern and Western Ghat mountain ranges experiences statistically significant decreasing trend. There are few ground-based observatories to verify satellite based trends for rural regions. However, using a past study and recent measurements we show a statistically significant decrease in NO_X and O₃ mixing ratio over a rural location (Gadanki; 13.48° N, 79.18° E) in South India. In the ground-based records of surface NO_X, the concentration during 2010–11 is found to be lower by 0.9 ppbv which is nearly 60 % of the values observed during 1994–95. Small but statistically significant decrease in noon-time peak ozone concentration is also observed. Noon-time peak ozone concentration has decreased from 34?±?13 ppbv during 1993–96 to 30?±?15 ppbv during 2010–11. NO_X mixing ratios are very low over Gadanki. In spite of low NO_X values (0.5 to 2 ppbv during 2010–11), ozone mixing ratios are not significantly low compared to many cities with high NO_X. The monthly mean ozone mixing ratio varies from 9 ppbv to 37 ppbv with high values during Spring and low values during late Summer. Using a box-model, we show that presence of VOCs is also very important in addition to NO_X in determining ozone levels in rural environment and to explain its seasonal cycle.     

Ozone Production Efficiency in Savanna and Forested Areas during the EXPRESSO Experiment

NO, NO_x, NO_y and O₃ have been measuredduring the airborne EXPRESSO experiment, November 96,which took place near Bangui (Central Africa) at thebeginning of the dry season. This period correspondsto an intense burning activity. Chemical andphotochemical characteristics of the planetaryboundary layer, which corresponds most of the time tothe monsoon layer, and the Harmattan layer, which issituated above the latter, have been studied forsavanna as well as rain forest areas. These two layersare very different when considering the chemicalcomposition (especially for ozone and NO_z) andthe photochemical age.The relationship of photochemical ozone productionversus photochemical NO_x oxidation products hasbeen investigated. Results indicate an ozoneproduction efficiency (OPE) ranging from 6.3 to 14.8in the planetary boundary layer. Thus, this layer ischaracteristic of a photochemically young and activeair mass. In this layer, the ozone potentialproduction increases with the air mass photochemicalage. On the other hand, the Harmattan layer shows anOPE ranging from 4.6 to 7.4. These values arecharacteristic of photochemically well-aged airmasses. In this layer, the ozone potential productionseems to be exhausted with values around 4.0 (i.e., 4ozone molecules produced for each NO_x moleculeemitted).     

华南地区春季平流层入侵对对流层低层臭氧影响的模拟研究

利用中尺度大气化学模式WRF/Chem对2013年3月6日华南地区一次平流层入侵事件及其对对流层低层臭氧的影响进行模拟研究。通过加入UBC（Upper Boundary Condition）上边界处理方案,弥补WRF/Chem模式未考虑平流层臭氧化学反应的不足。结合臭氧探空廓线资料、地面O₃、CO、NO_x、相对湿度、温度和风速等观测资料以及再分析资料对模拟结果进行定量评估,结果表明模式能较为真实地模拟本次平流层入侵过程。模拟分析进一步揭示:（1）副热带高空急流是本次平流层入侵的主要原因。当华南地区处在副热带急流入口区左侧下沉区域时,平流层入侵将富含臭氧的干燥空气输送到对流层中低层。（2）本次平流层入侵对对流层低层臭氧收支有重要影响,导致香港地区近地层臭氧体积混合比浓度明显上升,如塔门站夜间臭氧浓度升高21.3 ppb（1 ppb=1×10-9）。地面气象场和化学物种的分析进一步确认了平流层入侵的贡献。（3）采用动力学对流层顶高度时零维箱式模型和Wei公式计算得到的平流层入侵通量相当,分别为-1.42×10-3 kg m-2 s-1和-1.59×10-3 kg m-2 s-1,这一结果与前人研究相吻合,且与采用热力学对流层顶高度计算所得到的结果具有可比性。