中国地区臭氧前体物对地面臭氧的影响

利用GEOS-Chem模式的数值试验结果,研究中国地区NOx和两类VOCs对O3质量浓度分布及其化学机理的影响。研究表明,NOx的减少会使得中国西部O3质量浓度显著降低,但在冬季NOx的减少会使得东北、华北地区O3质量浓度上升。而京津唐地区由于VOCs/NOx比值偏低,不能通过单一减少NOx来控制O3质量浓度。VOCs排放的减少会使得我国东部地区O3质量浓度大幅减少,其中人为VOCs的减少能降低我国东部地面O3质量浓度,而生物VOCs的减少只能在夏秋季有效减少我国东部地区35°N以南区域的地面O3质量浓度。控制地面O3质量浓度时,中国西部主要考虑NOx的减排,东部35°N以北主要考虑AVOCs的减排,而30~35°N应同时考虑AVOCs和BVOCs的减排,在30°N以南的地区,则需要全面考虑NOx和VOCs的减排。     

鼎湖山森林地区臭氧及其前体物的变化特征和分析

通过对鼎湖山森林地区近地面O3和NOx浓度、太阳辐射、气象参数等为期一年的观测和资料分析,给出了地面O3和NOx浓度、太阳辐射的变化规律及其相互之间的关系.地面O3、NOx、CO、SO2浓度以及紫外辐射、太阳总辐射等有明显的日变化和季节变化.不同因子对O3的敏感性试验结果表明,晴天和实际天气,O3浓度对NO、NO2浓度的变化最为敏感,其次是水汽、气溶胶,最后是紫外辐射.所有因子的变化均引起O3在湿季比干季更大的变化率,因此在研究臭氧化学和光化学时,应该考虑水汽以及OH自由基的重要作用.对于晴天和实际天气的逐时值和日平均值而言,O3浓度与NO2/NO之间存在很好的正相关关系,比值NO2/NO可以作为判断O3峰值出现的一个指标.O3极值的出现既受NO和NOx影响,也受气象因素(温湿度、云、风、雾、降雨)和辐射的影响.周末O3、NOx浓度及NO2/NO有规律的增大,表明实验地点的大气受到人为污染源的影响.     

北京奥运会期间CBM-Z化学机制的模拟应用

利用CBM-Z化学机制模拟了中国科学院大气物理研究所气象塔站在北京奥运会期间高臭氧时段O3浓度的日变化,评估了气象条件、北京奥运会加强控制措施以及O3前体物浓度对近地面O3生成的影响。结果表明:(1)CBM-Z化学机制较好地模拟了北京奥运会期间典型时段气象塔站O3、NO、NO2日变化特征。(2)有利于局地高臭氧事件发生的气象条件非常相似;北京奥运会加强控制措施的实施显著减少了NOx及VOCs的排放量,导致近地面O3浓度的明显下降。(3)奥运会期间VOCs和CO是影响气象塔站O3生成量的关键因素。     

北京上甸子本底站2003年秋冬季痕量气体浓度变化特征

2003年9月至2004年2月在北京上甸子区域大气污染本底监测站(117°07′E,40°39′N,海拔293.9 m)开展了对大气中痕量气体的连续在线监测,获得了NO、NO2、SO2、CO和O3等气体组分的变化特征、变化规律和浓度水平。初步分析表明,NO、NO2、SO2、CO和O3有明显的日变化和月变化特征。O3浓度在秋季较高,冬季较低;NO、NO2和SO2冬季出现浓度高值。探讨了O3和痕量气体与气象因子的关系。O3与NO、NO2、NOx、CO和SO2皆为负相关,CO与NOx和SO2具有较好的相关性。本底站痕量气体浓度与同期观测的城区污染物浓度相比其变化趋势基本呈同位相。     

热带深对流云对CO、NO、NOx和O3的垂直输送作用

利用2005年11月至2006年2月ACTIVE (Aerosol and Chemical Transport in tropIcal conVEction) 外场试验期间在澳大利亚北部达尔文地区取得的CO、O3、NO和NOx飞机探测资料, 并结合HYSPLIT后向轨迹模式结果, 分析这几种气体成分在对流卷云砧内外的分布情况, 并探讨热带深对流云对于污染气体的垂直输送作用。分析结果显示, 在孤立对流云卷云砧中, 云砧内部O3、NO、NOx浓度均大于云外; 而CO则不同, 只有在近地面浓度高时才如此, 在近地面浓度较小时, 卷云砧内部的浓度反而小于云外。进一步分析造成这两类气体分布差异的原因, 发现CO主要借助深对流云将对流层下层以及对流云周围环境中的CO夹卷并动力垂直输送到对流云顶部卷云砧中, 而对于O3、NO和NOx来说, 除了上述作用以外, 还可能与对流云内部其他物理机制(如闪电), 造成新的O3、NO和NOx有关, 这些新生气体随着风暴内部强烈的上升气流被最终输送进云砧中。     

热带气旋影响下高臭氧污染的调控机理

利用美国环保局开发的第3代空气质量模式Models-3,对珠三角地区一次热带低压影响下的高臭氧空气污染事件进行了数值模拟,并通过一系列的一次污染物排放量的增减试验,探讨了不同的一次污染物排放情景,即采取不同的空气污染物的调控情况下,对珠三角地区低层臭氧生成的影响。研究结果表明,在热带低压影响下,要降低珠三角地区的日臭氧峰值,需采取的主要调控措施是控制氮氧化物的排放;或者随着氮氧化物的增长,相应增加生物源VOC(volatile organic compounds,易挥发有机化合物)的排放,以维持较高的VOC与NOx(氮氧化物)的比率。     

地面臭氧光化学过程规律的初步研究

给出了1996年夏季在广东肇庆鼎湖山对光化辐射、地面O3、NO、NO2浓度的观测结果,对影响地面O3、NO、NO2的主要因子进行了分析。晴天,地面O3、NO、NO2浓度有明显的日变化;阴天,它们的日变化比较复杂。晴天和阴天,在lnQUVB/m和lnQvis/m(其中QUVB为紫外B辐射,Qvis为可见光辐射,m为大气质量)与地面O3、NO,NO2浓度、整层大气水汽含量(q1、q2、q3、q4)之间存在着很好的相关关系。利用得到的关系式计算了地面O3浓度,在紫外和可见光波段,计算值与观测值符合得都比较好。     

华北地区一次强灰霾污染的天气学效应

利用在线耦合的大气化学模式WRF-Chem V3.6(Weather Research Forecasting Model with Chemistry Version 3.6)及环境、气象观测数据,在完成大气化学方案优选的基础上,研究了华北地区一次重霾污染过程(2013年2月15~17日)对气象条件的反馈作用。重点关注一次颗粒物、无机气态成分和挥发性有机污染物的人为排放对PM2.5(空气动力学当量直径小于等于2.5μm的颗粒物,即细颗粒物)生成的贡献,探讨了由此引发的气象条件的变化。模拟结果显示,上述3种人为源的综合排放对华北地区PM2.5浓度的平均贡献率为91.27%,其中对北京、秦皇岛和沧州的贡献率分别达96.9%、95.9%和97.2%。这使区域地面太阳向下短波辐射降低近15.99%,区域平均地面辐射强迫达-26.51 W m-2,由此导致地面温度下降0.14°C(3.68%),逆温增强,垂直温度梯度(?T/?z)升高0.026 K km-1,边界层高度降低18.92 m(8.77%),平均风速减少约0.014 m s-1(0.35%),相对湿度绝对值升高0.51%,地面平均气压降低0.86 Pa。对于15~17日污染过程,人为源综合排放的气溶胶对短波辐射的影响在天气过程中占主导地位,对边界层高度的影响较大,但不起主导作用,对温度、风速、相对湿度、气压的作用则远小于天气系统本身。挥发性有机污染物(Volatile Organic Compounds,VOCs)作为二次有机气溶胶(Secondary Organic Aerosol,SOA)的前体物,其人为排放对SOA浓度的贡献率约为99.6%。同时,VOCs通过调整大气反应活性促进无机气态成分向无机盐转化,它对硫酸盐和硝酸盐浓度的贡献达50%以上。然而,VOCs对整个PM2.5浓度的贡献不及各种源综合贡献的1/4。人为排放的VOCs对气象场的反馈与综合排放的作用基本一致,但对地面气压的影响VOCs排放时以热力因子为主,而人为源综合排放时以动力因子为主。上述结果暗示,灰霾污染过程所引发的气象条件向不利于污染物扩散方向改变,这可能促进污染物的局地累积、增强污染程度并延长区域内重污染的持续时间。因此,在探讨区域性灰霾污染成因时,灰霾自身通过辐射强迫作用对大气的调节是不可忽视的重要影响因素。     

北京秋季城区和近郊近地层O3特征

北京十三陵地区出现O3高值,一直是人们所关心的环境问题,秋季是北京地区高O3浓度季节,为此2001年9月7～17日在北京城区舞蹈学院楼顶和十三陵地区昭陵进行了一次以O3为主,并结合其前体物的综合比对实验.对北京城区和郊区地面O3特征进行了比对分析,目的是了解北京秋季近地面城乡O3差异的原因.结果表明郊区O3浓度日均值普遍大于城区O3日均值,城区和郊区白天O3浓度接近,城乡O3平均浓度的差异是由于不同天气条件下城区夜间地面O3浓度很低,有时甚至接近于零,而郊区夜间O3依然维持一定浓度.其主要原因在于城区有较多的污染排放源,致使夜间NO浓度维持相对高值,其通过滴定过程大量消耗O3所致.观测中发现无论城区或郊区当小时平均NO浓度大于10×10-9(体积混合比)时,相应小时平均O3浓度接近于零.NO2/NO低值区对应于地面O3低浓度,城区夜间NO2/NO值低于郊区.由此可见城区O3日平均值较低和城区空气污染重于郊区有密切关系.     

应用查表法模拟区域对流层O3、Nox分布和演化的研究

应用STEM-II气相光化学模式探讨了影响对流层O3、NOx气相光化学转化率的各物理、化学因子。表明在我国多数地区光化学污染物特征(NMHC/NOx较高)下,光辐射强度、温度、初始O3浓度和NOx浓度是影响O3、NOx气相光化学转化率的主要因子。将以上因子分档组合,计算并建立了各种情况下O3、NOx气相光化学转化率的查算表,并将之用于模拟区域O3、NOx的演化和分布。结果表明,与光化学模式直接耦合计算法相比,该方法既能显著缩短计算时间,又能基本反映大气化学反应的非线性过程,并与直接耦合法符合得较好。     

Anthropogenic Effects on Biogenic Secondary Organic Aerosol Formation

Anthropogenic emissions alter biogenic secondary organic aerosol(SOA) formation from naturally emitted volatile organic compounds(BVOCs). We review the major laboratory and field findings with regard to effects of anthropogenic pollutants(NOx, anthropogenic aerosols, SO_2, NH_3) on biogenic SOA formation. NOx participate in BVOC oxidation through changing the radical chemistry and oxidation capacity, leading to a complex SOA composition and yield sensitivity towards NOx level for different or even specific hydrocarbon precursors. Anthropogenic aerosols act as an important intermedium for gas–particle partitioning and particle-phase reactions, processes of which are influenced by the particle phase state, acidity, water content and thus associated with biogenic SOA mass accumulation. SO_2 modifies biogenic SOA formation mainly through sulfuric acid formation and accompanies new particle formation and acid-catalyzed heterogeneous reactions. Some new SO_2-involved mechanisms for organosulfate formation have also been proposed.NH_3/amines, as the most prevalent base species in the atmosphere, influence biogenic SOA composition and modify the optical properties of SOA. The response of SOA formation behavior to these anthropogenic pollutants varies among different BVOCs precursors. Investigations on anthropogenic–biogenic interactions in some areas of China that are simultaneously influenced by anthropogenic and biogenic emissions are summarized. Based on this review, some recommendations are made for a more accurate assessment of controllable biogenic SOA formation and its contribution to the total SOA budget. This study also highlights the importance of controlling anthropogenic pollutant emissions with effective pollutant mitigation policies to reduce regional and global biogenic SOA formation.     

Evaluation of the use of photochemical indicators to assess ozone—NOx—VOC sensitivity in the Southwestern Iberian Peninsula

Understanding the chemical links between ozone (O₃) and its two main precursors, nitrogen oxides (NOx) and volatile organic compounds (VOC), is important for designing effective photochemical smog reduction strategies. This chemical relationship will determine which precursor (NOx or VOC) emission reduction will be more effective for decreasing the ozone formation. Under certain conditions, ozone levels decrease as a result of a reduction in NOx emissions but do not respond significantly to changes in VOC emissions (NOx-sensitive condition), while under other conditions ozone concentrations decrease in response to reductions in VOCs and may even increase when NOx emissions are reduced (VOC-sensitive conditions). Indicator species can be used to assess the sensitivity of ozone to changes in the emissions of its precursors. These indicators are species or species ratios involved in ozone photochemistry which reflect the primary chemical process through which the ozone was formed. In this work we use the MM5-CAMx model system to explore the behaviour of various indicator species during two meteorological situations featuring different atmospheric conditions in a complex terrain area. The results show that indicators based on nitrogen compounds (i.e,. NOy and NOz) are suitable for defining the transition range from VOC- to NOx-sensitive chemistry, and that despite the uncertainties associated with the use of chemical indicators, the ratios O₃/NOy and O₃/NOz may provide a simple and useful way to summarize the response of ozone to changes in NOx and VOC emissions in Southwestern Spain.     

BVOC emissions from mechanical wounding of leaves and branches of <Emphasis Type="Italic">Eucalyptus sideroxylon</Emphasis> (red ironbark)

Emissions of biogenic volatile organic compounds (BVOCs) from mechanical wounding of leaves and branches of plants can contribute to the atmospheric burden of volatile organic compounds (VOCs) in both (a) urban airsheds (from urban garden maintenance) and (b) the global atmosphere (from large scale forest harvesting). These emissions of BVOCs are poorly understood and quantified, and their role in urban and global emissions inventories neglected. This paper presents measurements of the magnitude, duration and composition of emissions of BVOCs, carbon dioxide (CO₂) and methane (CH₄) from freshly cut leaf mulch and wood chips derived from a common eucalypt tree, Eucalyptus sideroxylon (red ironbark), found in southeastern Australian forests and gardens. The emissions of BVOCs from freshly cut and shredded leaves and wood of E. sideroxylon were found to be 2.3 ± 0.6 and 0.05 ± 0.04 mg g^-1 DM (Dry Mass) from leaf mulch and wood chips respectively and to last typically for 1 day following cutting. Three sampling techniques were used for VOC speciation and the 12 most abundant BVOCs released from the mulch materials were identified. The specific BVOCs emitted in order of decreasing abundance from leaf mulch are: (a) stored plant oils, 1,8-cineole, α–pinene and o-cymene which make up the major part of the emissions, (b) a minor contribution from chemicals associated with environmental stress and wound defence, (Z)–3–hexenyl acetate, (E)-2-hexenal and (Z)-3-hexen-1-ol, and (c) a second minor contribution from metabolic products, acetaldehyde and acetone. The observed integrated emissions of BVOCs from leaves following mulching are equivalent to more than half and perhaps all of the likely stored plant oils in the leaves. For the two comparable studies available, one of a plant with stored oils (this study) and one of a plant without stored plant oils, the emissions of leaf wound defence BVOCs are in the same range for both plants. In the plant with stored plant oils, the plant oil emissions are about a factor of 11 larger in emission rate than the plant wound defence BVOCs. A compilation of available leaf wounding BVOC emission studies indicates that for plants with stored plant oils, plant oil emissions dominate, whereas with other plants, leaf wound defence BVOCs dominate the emissions.     

Spatial and Temporal Distributions and Sources of Anthropogenic NMVOCs in the Atmosphere of China: A Review

As the key precursors of O_3, anthropogenic non-methane volatile organic compounds(NMVOCs) have been studied intensively. This paper performed a meta-analysis on the spatial and temporal variations of NMVOCs, their roles in photochemical reactions, and their sources in China, based on published research. The results showed that both nonmethane hydrocarbons(NMHCs) and oxygenated VOCs(OVOCs) in China have higher mixing ratios in the eastern developed cities compared to those in the central and western areas. Alkanes are the most abundant NMHCs species in all reported sites while formaldehyde is the most abundant among the OVOCs. OVOCs have the highest mixing ratios in summer and the lowest in winter, which is opposite to NMHCs. Among all NMVOCs, the top eight species account for 50%-70% of the total ozone formation potential(OFP) with different compositions and contributions in different areas. In devolved regions, OFP-NMHCs are the highest in winter while OFP-OVOCs are the highest in summer. Based on positive matrix factorization(PMF) analysis, vehicle exhaust, industrial emissions, and solvent usage in China are the main sources for NMHCs. However, the emission trend analysis showed that solvent usage and industrial emissions will exceed vehicle exhaust and become the two major sources of NMVOCs in near future. Based on the meta-analysis conducted in this work,we believe that the spatio-temporal variations and oxidation mechanisms of atmospheric OVOCs, as well as generating a higher spatial resolution of emission inventories of NMVOCs represent an area for future studies on NMVOCs in China.     

Characterization and source apportionment of volatile organic compounds in urban and suburban Tianjin,China

Tianjin is the third largest megacity and the fastest growth area in China, and consequently faces the problems of surface ozone and haze episodes. This study measures and characterizes volatile organic compounds(VOCs), which are ozone precursors, to identify their possible sources and evaluate their contribution to ozone formation in urban and suburban Tianjin,China during the Ha Chi(Haze in China) summer campaign in 2009. A total of 107 species of ambient VOCs were detected,and the average concentrations of VOCs at urban and suburban sites were 92 and 174 ppbv, respectively. Of those, 51 species of VOCs were extracted to analyze the possible VOC sources using positive matrix factorization. The identified sources of VOCs were significantly related to vehicular activities, which specifically contributed 60% to urban and 42% to suburban VOCs loadings in Tianjin. Industrial emission was the second most prominent source of ambient VOCs in both urban and suburban areas, although the contribution of industry in the suburban area(36%) was much higher than that at the urban area(16%). We conclude that controlling vehicle emissions should be a top priority for VOC reduction, and that fast industrialization and urbanization causes air pollution to be more complex due to the combined emission of VOCs from industry and daily life, especially in suburban areas.     

近地面臭氧研究进展

近地面臭氧是空气中氮氧化物和挥发性有机物发生光化学反应的产物,其浓度与气象条件密切相关。晴天少云、紫外辐射较强、温度较高、相对湿度较低以及风速较小的天气,均有利于臭氧的生成,其中紫外辐射是产生臭氧最关键的因素。臭氧前体物（氮氧化物和挥发性有机物）的浓度及其比值是影响近地面臭氧浓度的另外三个重要因素。我国大多数城市的O3处于VOC控制区,即NOx浓度的增加会引起O3浓度的降低,而VOCs浓度的增加则会使其浓度升高。因而VOC源解析问题成为近年来O3研究的一个热点问题。同时,由于气溶胶可以直接吸收、散射太阳紫外辐射、短波辐射以及大气长波辐射,因此气溶胶的存在会影响大气中光化学反应的进程,从而影响臭氧的光化学生成,气溶胶对近地面臭氧的影响已成为目前大气环境的前沿课题。     

COVID-19疫情期间全球空气质量变化:臭氧响应的区域间差异

疫情期间全球各地一次排放大幅削减,而臭氧等二次污染的响应则存在着区域间差异.结合地面和卫星观测发现,同在氮氧化物大幅下降的情况下,臭氧在东亚和欧洲呈现出可达14ppb的上升信号,而北美则下降为主(约2-4ppb).我们结合气象分析和臭氧敏感性进一步讨论了臭氧响应差异性的原因,一方面受臭氧与前体物间关系的影响;另一方面来自于气象,尤其是温度.研究明晰了人为排放,化学和气象三者的内在关联,强调了在臭氧控制过程中考虑前体物削减和气象条件协同的重要性.     

2017年8—9月湖州市臭氧污染特征及其生成机制研究

近年来近地面臭氧问题日益凸显,成为影响空气质量持续改善的瓶颈.本研究基于2017年8—9月在湖州市城区开展的为期1个月的臭氧及其前体物挥发性有机物（VOCs）和氮氧化物（NO_x）在线观测数据,分析了臭氧及其前体物污染特征,利用正矩阵因子分析（PMF）解析了VOCs来源,并采用基于观测的模型（OBM）对臭氧生成机制进行研究.研究结果表明：1）观测期间湖州市VOCs平均体积分数为（24.78±9.10）×10^-9,其中占比最高的组成为烷烃、含氧VOCs （OVOCs）和卤代烃;2）在臭氧非超标时段,湖州市臭氧生成处于VOCs控制区,而在臭氧重污染期间湖州市处于以VOCs控制为主的过渡区;3）在臭氧超标时段,对臭氧生成潜势（OFP）贡献最大的是芳香烃（39.6%）,其次是烯烃（21.5%）和OVOCs （19.4%）,排名前三的关键组分为甲苯、乙烯和间/对二甲苯;4）源解析结果显示观测期间湖州市VOCs的主要来源是溶剂使用（27.0%）、交通排放（22.7%）、背景+传输（19.3%）、工业排放（16.9%）、汽油挥发（7.7%）和植物排放（6.4%）,重污染过程期间对OFP贡献最大的两类源是交通排放源和溶剂使用源,贡献百分比分别为35.1%和30.5%.因此,对交通排放和溶剂使用方面进行控制管理对湖州市大气臭氧污染防控有重要意义.     

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.