南京地区大气颗粒物影响近地面臭氧的个例研究

通过对2008年4月2～7日南京地区地面气象观测数据以及两个站点空气质量(O₃、NO_x、PM10)监测资料的分析, 发现O₃和PM10之间存在一定程度的反相关。利用一个光化学箱模式对该个例中大气颗粒物影响近地面臭氧的过程进行模拟, 结果发现大气颗粒物浓度的升高使得气溶胶光学厚度增加20％～40%, 导致NO₂和O₃近地面光解率下降20%～30%, OH和HO₂自由基浓度分别减少20%～50%, 造成O₃净生成率下降30%～40%。研究表明, 颗粒物对光化学过程的抑制造成了大气氧化能力的降低, 是近地面臭氧浓度减少的可能原因。     

北京秋季一次典型大气污染过程多站点分析

多站点多种大气污染物的同步在线观测对深入剖析大气污染的成因和演变机制有重要意义。以龙潭湖、北京325 m塔、双清路和阳坊4监测站点实时NO_x、SO₂、O₃、PM2.5和PM10浓度观测数据为基础,介绍了北京地区2010年10月3～11日发生的一次典型污染过程。不同污染物在污染过程中变化特征不一致,表现为NO_x、SO₂、O₃浓度有明显日变化,而PM浓度升高后一直维持在高值,日变化幅度很小。通过分析不同站点、相同污染物之间的相关性和变异系数发现,4站点间一次污染物NO和SO₂空间浓度差别大,变异系数分别为77%和70%,相关系数低于0.44;而二次污染物NO₂、PM2.5、O₃空间浓度差别较小,变异系数分别为34%、36%和29%,相关系数均超过0.54。结合中尺度气象模式研究发现,该污染过程中,850 hPa高空持续的西南暖平流造成华北地区显著平流逆温,与近地层辐射逆温共同作用,使北京地区混合层高度维持在1200 m以下。低混合层高度和低风速限制了大气垂直和水平扩散,造成北京地区近地层污染物累积,形成重度污染。     

金华地区夏秋大气中过氧乙酰硝酸酯的污染特征

过氧乙酰硝酸酯（PAN）是由VOCs和NO_x的光化学反应生成的一种典型二次污染物,比O₃更适合作为光化学污染的指示剂.2019年6—10月对浙江中部盆地金华市大气中PAN进行了在线监测,并对影响其体积分数变化的因素进行了分析,同时还分析了一次典型的光化学污染过程.结果表明,观测期间PAN的平均体积分数为0.656×10^-9,最高体积分数为4.348×10^-9,日均体积分数水平在0.130×10^-9~2.203×10^-9之间.PAN日变化特征显著,9月为明显的双峰变化,其他月份均为单峰.受气象条件的影响,夏季的污染程度显著低于秋季.9月27—30日典型污染时段内,PAN的小时均值是整个观测期均值的2.8倍,污染以本地积累为主.前体物浓度水平差异与去除机制的不同是影响PAN和O₃相关性的重要因素,此外NO/NO₂的比值是影响PAN生成速率的重要因素,PAN的峰值基本出现在NO/NO₂比值较低的时段.在生成PAN的VOCs物种中,丙烷、乙烷和间/对二甲苯所占比例较大.     

2016年冬季南京地区大气污染特征的观测分析

基于2016年11月24日—12月23日南京市草场门站、鼓楼站和仙林站的强化试验观测资料,分析了城市和郊区主要大气污染物的时空变化特征及其与气象要素的相互关系。研究发现：观测期间南京PM_2.5、PM₁₀、NO₂、O₃、CO、SO₂月均质量浓度分别为52.84~84.34 μg·m^-3、88.36~120.34 μg·m^-3、49.98~51.66 μg·m^-3、24.85~50.57 μg·m^-3、0.99~1.2 mg·m^-3和22.1~26.48 μg·m^-3;近地面,城市大气污染物质量浓度高于郊区,其中城市O₃比郊区高61.0%;在城市地区,除NO₂和CO外,鼓楼站大气污染物质量浓度高于草场门站,其中鼓楼站PM_2.5比草场门站高42.7%;PM_2.5小时质量浓度最大为210.93 μg·m^-3,重污染过程出现时风速较低、温度较高,郊区PM₁₀、PM_2.5、NO₂质量浓度呈现高值时的最频风向为南风,O₃和SO₂质量浓度呈现高值时的最频风向分别为西风和西南风,所以郊区大气污染受城市输送影响。利用HYSPLIT模式研究发现12月4—8日和16—20日的污染气团分别来自西部和北方地区,聚类分析发现12月影响南京市的污染气团45%来自西部地区且移动速度较快,55%来自北方地区且移动速度较慢。由此可见,南京市冬季出现的大气污染,其形成不仅与本地排放和局地气象条件有关,而且西部和北方地区的远距离输送也会造成影响。     

大气化学研究的若干进展

近年来,大气化学研究工作有着飞跃的发展,现就其中若干方面简介如下: 一、对现今大气的组成、污染物地面浓度以及它们的来源有了新的资料和认识,特别是对背景大气中许多痕量气体,如NH₃、HNO₃、O₃、HCN、CH₄、CO、NO_x、H₂S、SO₂、H₂SO₄、HCl、HNO₂和CH₃Cl等等,有了新的定量资料。这是一大批现代的物理、化学分析等测试方法得到运用的结果。     

三亚地区冬春季大气污染特征观测研究

为了研究海南省三亚地区冬春季大气污染状况,于2011年12月—2013年4月的冬春季节在三亚鹿回头村(监测点位于三亚市郊,三面临海,周围没有工业污染源)开展了大气主要污染物(NO_x、O₃、PM_2.5)的连续监测,利用观测数据对三亚地区冬春季大气污染变化特征进行分析.结果表明:三亚地区大气污染物浓度均低于国家一级标准的浓度值,NO、NO₂、NO_x、O₃、PM_2.5质量浓度的日平均值(平均值±标准差)分别为(2.1±2.2)、(5.2±3.4)、(7.3±3.8)、(59.8±28.4)和(17.5±14.3)μg·m^-3.在污染物的日变化方面,NO_x、PM_2.5呈现典型的双峰型,其峰值分别出现在08:00和17:00,峰谷在13:00;O₃的日变化为单峰型,峰值出现在13:00.通过后向轨迹分析发现,三亚地区大气污染物受局地源排放和外源输送的共同影响,来自陆地的气流易造成污染物的积累,而来自海上的气流则有利于污染物的清除.     

北京夏季O3日变化及通量研究

2002年夏季,以北京325m气象塔为观测平台,进行了大气污染物臭氧(O₃)及其前体物氮氧化物(NO_x)和气象要素加强期的同步观测,并对观测资料做了详尽分析。结果表明:边界层内存在明显的臭氧浓度垂直差异;低层(120m)O₃浓度呈明显的日变化,且昼夜振幅较大;夜间高层(280m)O₃的化学消耗较弱,可维持较高的浓度;稳定度(Ri)在低层以中性态居多,振幅较小,而在高层以不稳定态居多,振幅较大。两层O₃湍流输送通量都呈单峰变化。白天,在O₃前体物和局地光化学反应共同作用下,120m左右处的O₃污染最大。     

中国区域大气本底站近地面臭氧来源贡献及区域代表性

回顾了关于长距离输送对中国区域本底大气臭氧的影响,以及中国区域大气本底站臭氧变化及其区域代表性两方面的研究进展。来自不同污染源区O₃的长距离输送对中国区域O₃影响的研究结果分歧较大,贡献最显著的源区和受体地区也存在争议;同时,鲜有研究考虑到平流层对对流层的O₃贡献,而这部分贡献在前体物排放很少的本底地区非常重要。中国区域各大气本底观测站分别与其周围一定范围内的区域具有相同的对流层O₃柱浓度最大值月份分布,而对与人体健康密切相关的近地面O₃区域特征的分析尚未深入开展;鉴于研究方法的局限性,也尚未深入揭示形成O₃变化区域特征的复杂成因。基于现有研究进展和不足之处,如何利用全球大气化学-环流模式的示踪模拟结果,定量评估来自全球不同地区的O₃对中国本底大气O₃的影响,并进一步评估中国区域6个大气本底站近地面O₃季节变化的区域代表性,是亟待解决的科学问题。     

基于CMAQ-MCM模型的长三角地区夏季臭氧和大气氧化性影响的研究

传统的空气质量模型多使用简化的光化学反应机制来模拟大气污染物的形成.这些机制主要基于烟雾箱实验拟合的反应速率和产物来模拟二次产物（如臭氧（O₃））前体物的氧化反应,具有一定的不确定性,导致模拟结果产生偏差.针对该问题,本研究将详细的大气化学机理（MCMv3.3.1）与美国国家环境保护局研制的第三代空气质量预报和评估系统CMAQ相结合（CMAQ-MCM）,模拟研究长三角地区2015年8月27—9月5日臭氧高发时段的空气质量.CMAQ-MCM模型可以较好地模拟长三角地区6个代表城市O₃和其前体物随时间的变化趋势.对模拟的O₃日最大8 h平均浓度的统计分析表明,徐州表现最好（标准平均误差=-0.15,标准平均偏差=0.23）.在长三角地区,居民源对挥发性有机物（VOCs）的贡献最大,占39.08%,其次是交通运输（33.25%）和工业（25.56%）.能源对总VOCs的贡献最小,约为2.11%.对活性氧化氮（NO_y）的分析表明,其主要组分是NO_x（80%）,其次是硝酸（HNO₃）（<10%）.O₃的空间分布与NO_y和NO_x非常相似.HCHO等其他氧化产物的分布与NO_x相似,这很可能是由于在高NO_x条件下VOCs氧化产生的产物.甲基乙烯基酮（MVK）和甲基丙烯醛（MACR）的空间分布与自然源VOCs （BVOCs）非常相似,表明长三角地区MVK和MACR主要由BVOCs氧化生成.长三角地区受到人为源和自然源排放相互作用的影响.     

基于空气质量模拟的江苏省大气污染物排放清单比较研究

大气污染物排放清单是空气质量模拟和空气污染治理的重要依据.本研究比较分析了两套覆盖江苏省的2017年大气污染物排放清单，即分别由上海市环境科学研究院、江苏省环境科学研究院编制的"长三角清单"和"江苏省清单"，并结合区域空气质量模型CMAQ评估不同清单对长三角地区2017年1、4、7、10月的空气质量模拟的影响.清单比较结果表明，除二氧化硫（SO₂）以外，江苏省清单估算的各污染物排放量较长三角清单低.通过与观测数据比较，发现两套清单对SO₂、氮氧化物（NO_x）、臭氧（O₃）和细颗粒物（PM_2.5）的模型模拟性能均较好.江苏省清单与长三角清单两者的模拟结果空间分布接近，其中江苏省清单模拟的PM_2.5和O₃在长三角多数地区略低于长三角清单的模拟结果（1月O₃除外）.江苏省清单与长三角清单均能够用于空气质量模式模拟，可为江苏地区的细颗粒物和光化学烟雾污染的控制策略制定提供参考.     

龙凤山大气近地层O3浓度变化及与其它因素的关系

研究首次在龙凤山区域大气本底站测得的地面Ｏ３浓度及其变化的资料表明,中国东北农村地面大气Ｏ３浓度总体水平不很高,但在少数特殊的天气条件下,时均浓度可超过国家二级标准。Ｏ３浓度存在明显的季节和日变化,其月平均浓度１９９５年１月最低（２７．５ｐｐｂ）,１９９４年１１月最高（４３．２ｐｐｂ）。Ｏ３日变化幅度夏季的晴天最大（２８ｐｐｂ）,冬季的阴天最小（８ｐｐｂ）。气象要素（尤其是风速、气温和相对湿度等）和ＮＯｘ与地面Ｏ３浓度有较密切的关系。用多变量分析法探讨了地面Ｏ３各指标随气象因子和ＮＯｘ共同变化的规律,并拟合了寒冷和温暖期里与地面Ｏ３日最高浓度、日最低浓度及日变化幅度有关的方程。     

Impact of Non-Methane Hydrocarbons on Tropospheric Chemistry and the Oxidizing Power of the Global Troposphere: 3-Dimensional Modelling Results

The impact of natural and anthropogenicnon-methane hydrocarbons (NMHC) on troposphericchemistry is investigated with the global,three-dimensional chemistry-transport model MOGUNTIA.This meteorologically simplified model allows theinclusion of a rather detailed scheme to describeNMHC oxidation chemistry. Comparing model resultscalculated with and without NMHC oxidation chemistryindicates that NMHC oxidation adds 40–60% to surfacecarbon monoxide (CO) levels over the continents andslightly less over the oceans. Free tropospheric COlevels increase by 30–60%. The overall yield of COfrom the NMHC mixture considered is calculated to beabout 0.4 CO per C atom. Organic nitrate formationduring NMHC oxidation, and their transport anddecomposition affect the global distribution of NO _x and thereby O₃ production. The impact of theshort-lived NMHC extends over the entire tropospheredue to the formation of longer-lived intermediateslike CO, and various carbonyl and carboxyl compounds.NMHC oxidation almost doubles the net photochemicalproduction of O₃ in the troposphere and leads to20–80% higher O₃ concentration inNO _x -rich boundarylayers, with highest increases over and downwind ofthe industrial and biomass burning regions. Anincrease by 20–30% is calculated for the remotemarine atmosphere. At higher altitudes, smaller, butstill significant increases, in O₃ concentrationsbetween 10 and 60% are calculated, maximizing in thetropics. NO from lightning also enhances the netchemical production of O₃ by about 30%, leading to asimilar increase in the global mean OH radicalconcentration. NMHC oxidation decreases the OH radicalconcentrations in the continental boundary layer withlarge NMHC emissions by up to 20–60%. In the marineboundary layer (MBL) OH levels can increase in someregions by 10–20% depending on season and NO _x levels.However, in most of the MBL OH will decrease by10–20% due to the increase in CO levels by NMHCoxidation chemistry. The large decreases especiallyover the continents strongly reduce the markedcontrasts in OHconcentrations between land and oceanwhich are calculated when only the backgroundchemistry is considered. In the middle troposphere, OHconcentrations are reduced by about 15%, although dueto the growth in CO. The overall effect of thesechanges on the tropospheric lifetime of CH₄ is a 15%increase from 6.5 to 7.4 years. Biogenic hydrocarbonsdominate the impact of NMHC on global troposphericchemistry. Convection of hydrocarbon oxidationproducts: hydrogen peroxides and carbonyl compounds,especially acetone, is the main source of HO _x in theupper troposphere. Convective transport and additionof NO from lightning are important for the O₃ budgetin the free troposphere.     

A vertical profile of Ozone concentration in the atmosphericboundary layer over central Taiwan

Summary  In the central region of Taiwan, ozone episodes occur most often during autumn. Two field experiments were conducted during the autumns of 1998 and 1999 to analyze the vertical profile of the boundary layer and determine its effects on ozone concentration over the region. The vertical virtual potential temperature and wind profiles were derived from tethersonde data. The NO_x, NMHC and O₃ concentration vertical profiles were monitored up to a height of 500 meters using black-covered Teflon tedler sampling bags. During the experimental periods, nighttime terrestrial long wave radiation could cause the inversion height to reach 500 meters by the following morning. It was shown that these types of synoptic structures suppress the vertical diffusion of NO_x, NMHC and O₃. During the daytime, measurements indicate that pollutants were well mixed in the upper portion of the mixing layer. At night, the ground level ozone concentration was on the decrease but increased with altitude to a height of 500 m. The NO_x decreased with altitude whereas the NMHC showed no significant variations. Received April 13, 2000 Revised July 24, 2000     

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.     

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.     

闪电产生氮氧化物对青藏高原臭氧低谷形成的影响

为了进一步了解青藏高原闪电的产生氮氧化物（LNO_x）经由光化学反应对O₃浓度变化及夏季O₃低谷形成的可能影响,本文利用2005~2013年由OMI卫星得到的对流层NO₂垂直浓度柱（NO₂ VCD）、O₃总浓度柱（TOC）和O₃廓线以及星载光学瞬变探测器OTD和闪电成像仪LIS获取的总闪电数资料,对青藏高原和同纬度长江中下游地区的TOC和NO₂ VCD月均值时空分布特征、闪电与NO₂ VCD的相关性和O₃的垂直分布特征及其与LNO_x的关系进行了对比分析。结果表明,青藏高原的O₃低谷主要出现在夏季和秋季,其TOC值比同纬度长江中下游地区低约10~15 DU（Dobson unit）。青藏高原NO₂VCD总体较小,表现为夏高冬低的分布特征。青藏高原夏季O₃浓度受南亚高压的影响总体呈减小趋势,但因强雷暴天气导致对流层中上部LNO_x浓度升高,并随强上升气流向对流层顶输送,同时通过光化学反应使O₃浓度增加,缩小了青藏高原和同纬度地区的O₃浓度差,减缓了O₃总浓度的下降,抑制了夏季O₃低谷的进一步深化。     

NOx or VOC Limitation in East German Ozone Plumes?

The ozone forming potential of VOCs and NO_x for plumes observed from several cities and a power plant in eastern Germany was investigated. A closed box model with a gas phase photochemical reaction mechanism was employed to simulate several scenarios based upon aircraft observations. In several of the scenarios, the initial concentrations of NO_x, VOCs, and SO₂, were reduced to study the factors limiting the O₃ production. Ozone production was limited by the initial VOC concentrations for all of the simulated plumes. Higher O₃ concentrations were produced with reduced initial NO_x. In one sample with high SO₂ mixing ratios (>100 ppb), SO₂ was also identified as a significant contributor to the production of O₃.     

Numerical study of the oxidation process of dimethylsulfide in the marine atmosphere

A box model, involving simple heterogeneous reaction processes associated with the production of non-sea-salt sulfate (nss-SO ₄ ^2– ) particles, is used to investigate the oxidation processes of dimethylsulfide (DMS or CH₃SCH₃) in the marine atmosphere. The model is applied to chemical reactions in the atmospheric surface mixing layer, at intervals of 15 degrees latitude between 60° N and 60° S. Given that the addition reaction of the hydroxyl radical (OH) to the sulfur atom in the DMS molecule is faster at lower temperature than at higher temperature and that it is the predominant pathway for the production of methanesulfonic acid (MSA or CH₃SO₃H), the results can well explain both the increasing tendency of the molar ratio of MSA to nss-SO ₄ ^2– toward higher latitudes and the uniform distribution with latitude of sulfur dioxide (SO₂). The predicted production rate of MSA increases with increasing latitude due to the elevated rate constant of the addition reaction at lower temperature. Since latitudinal distributions of OH concentration and DMS reaction rate with OH are opposite, a uniform production rate of SO₂ is realized over the globe. The primary sink of DMS in unpolluted air is caused by the reaction with OH. Reaction of DMS with the nitrate radical (NO₃) also reduces DMS concentration but it is less important compared with that of OH. Concentrations of SO₂, MSA, and nss-SO ₄ ^2– are almost independent of NO _x concentration and radiation field. If dimethylsulfoxide (DMSO or CH₃S(O)CH₃) is produced by the addition reaction and further converted to sulfuric acid (H₂SO₄) in an aqueous solution of cloud droplets, the oxidation process of DMSO might be important for the production of aerosol particles containing nss-SO ₄ ^2– at high latitudes.     

RESEARCH ON SURFACE O3 WITH METEOROLOGICAL CONDITIONS UNDER ATMOSPHERIC BACKGROUND CONDITIONS IN NORTHEAST CHINA*

Surface O₃ concentration and its precursors have been observed at Longfengshan station,Heilongjiang Province for a period of one year from August 13,1994 to July 30,1995. Relationship between surface O₃ and the meteorological conditions during this period is analyzed in this study.Observation results show that diurnal variation of surface O₃ follows a pattern of double-peaks with amplitude of 27-28 ppb under fine days in summer and autumn.Although the diurnal variation is small(14 ppb),it is still detectable when it is overcast.Diurnal variation of O₃ is irregular under rainy days.Surface O₃ concentration rises when wind speed starts to increase at 0800 BT(Beijing Time)from 0 to 6 m s^-1in autumn,winter and summer.Relative high surface O₃ concentration is noticed frequently when S,SSW,SW and WSW wind are encountered at the station during all seasons.At 0800 BT and 1400 BT the surface O₃ concentration increases with the increase of global radiation accordingly during fine days in winter,spring and autumn.During fine days average peak of O₃ concentration in summer is 20 ppb higher than that in winter while the average peak of global radiation in summer is almost twice as high as that in winter.The average surface O₃ concentration under fine days in autumn at Longfengshan station is 14 ppb lower in comparison to the observation results from Lin'an station where Lin'an is at about the same longitude and lower latitude,with same environment,which is mainly caused by the difference of global radiation due to different latitudes in these two areas(difference of average peak global radiation about 100 W m^-2).     

Simulations of seasonal variations of sulfur compounds in the remote marine atmosphere

A photochemical box model is used to simulate seasonal variations in concentrations of sulfur compounds at latitude 40° S. It is assumed that the hydroxyl radical (OH) addition reaction to sulfur in the dimethyl sulfide (DMS) molecule is the predominant pathway for methanesulfonic acid (MSA) production, and that the rate constant increases as the air temperature decreases. Concentration of the nitrate radical (NO₃) is a function of the DMS flux, because the reaction of DMS with NO₃ is the most important loss mechanism of NO₃. While the diurnally averaged concentration of OH in winter is a factor of about 8 smaller than in summer, due to the weak photolysis process, the diurnally averaged concentration of NO₃ in winter is a factor of about 4–5 larger than in summer, due to the decrease of DMS flux. Therefore, at middle and high latitudes in winter, atmospheric DMS is mainly oxidized by the reaction with NO₃. The calculated ratio of the MSA to SO₂ production rates is smaller in winter than in summer, and the MSA to non-sea-salt sulfate (nssSO₄ ^2-) molar ratio varies seasonally. This result agrees with data on the seasonal variation of the MSA/nssSO₄ ^2- molar ratio obtained at middle and high latitudes. The calculations indicate that during winter the reaction of DMS with NO₃ is likely to be a more important sink of NO_x (NO+NO₂) than the reaction of NO₂ with OH, and to serve as a significant pathway of the HNO₃ production. If dimethyl sulfoxide (DMSO) is produced through the OH addition reaction and is heterogeneously oxidized in aqueous solutions, half of the nssSO₄ ^2- produced in summer may be through the oxidation process of DMSO. It is necessary to further investigate the oxidation products by the reaction of DMS with OH, and the possibility of the reaction of DMS with NO₃ during winter.