Analysis of the Effect of Optical Properties of Black Carbon on Ozone in an Urban Environment at the Yangtze River Delta,China

Black carbon(BC) reduces the photolysis coefficient by absorbing solar radiation, thereby affecting the concentration of ozone(O_3) near the ground. The influence of BC on O_3 has thus received much attention. In this study, Mie scattering and the tropospheric Ultraviolet and Visible radiation model are used to analyze the effect of BC optical properties on radiation. Combined with data of O_3 precursors in Nanjing in 2014, an EKMA curve is drawn, and the variations in O_3 concentration are further investigated using a zero-dimensional box mechanism model(NCAR MM). When O_3 precursors are unchanged, radiation and O_3 show a highly similar tendency in response to changing BC optical properties(R=0.997).With the increase of modal radius, the attenuation of fresh BC to radiation and O_3 first trends upward before decreasing. In the mixing process, the attenuation of BC to radiation and O_3 presents an upward tendency with the increase of relative humidity but decreases rapidly before increasing slowly with increasing thickness of coating. In addition, mass concentration is another major factor. When the BC to PM2.5 ratio increases to 5% in Nanjing, the radiation decreases by approximately 0.13%–3.71% while O_3 decreases by approximately 8.13%–13.11%. The radiative effect of BC not only reduces O_3 concentration but also changes the EKMA curve. Compared with the NOx control area, radiation has a significant influence on the VOCs control area. When aerosol optical depth(AOD) increases by 17.15%, the NOx to VOCs ratio decreases by 8.27%, and part of the original NOx control area is transferred to the VOCs control area.     

ROx Budgets and O3 Formation during Summertime at Xianghe Suburban Site in the North China Plain

Photochemical smog characterized by high concentrations of ozone (O3) is a serious air pollution issue in the North China Plain (NCP) region, especially in summer and autumn. For this study, measurements of O3, nitrogen oxides (NOx), volatile organic compounds (VOCs), carbon monoxide (CO), nitrous acid (HONO), and a number of key physical parameters were taken at a suburban site, Xianghe, in the NCP region during the summer of 2018 in order to better understand the photochemical processes leading to O3 formation and find an optimal way to control O3 pollution. Here, the radical chemistry and O3 photochemical budget based on measurement data from 1-23 July using a chemical box model is investigated. The daytime (0600-1800 LST) average production rate of the primary radicals referred to as ROx (OH + HO2+ RO2) is 3.9 ppbv h-1. HONO photolysis is the largest primary ROx source (41％). Reaction of NO2 + OH is the largest contributor to radical termination (41％), followed by reactions of RO2 + NO2 (26％). The average diurnal maximum O3 production and loss rates are 32.9 ppbv h-1 and 4.3 ppbv h-1, respectively. Sensitivity tests without the HONO constraint lead to decreases in daytime average primary ROx production by 55％ and O3 photochemical production by 42％, highlighting the importance of accurate HONO measurements when quantifying the ROx budget and O3 photochemical production. Considering heterogeneous reactions of trace gases and radicals on aerosols, aerosol uptake of HO2 contributes 11％ to ROx sink, and the daytime average O3 photochemical production decreases by 14％. The O3-NOx-VOCs sensitivity shows that the O3 production at Xianghe during the investigation period is mainly controlled by VOCs.     

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.     

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(NOx)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。     

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.     

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.     

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。     

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。     

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.     

2018年北京城区和远郊区低层大气风场特征分析

利用2018年1月1日至12月31日在北京国家综合气象观测实验基地获得的风廓线雷达资料和同时期在河北香河的华北香河全大气层野外科学观测研究站获得的多普勒声雷达资料,比较分析北京城区和远郊区的低层（0～600 m）大气风场特征。结果表明:水平风速随高度增加而增大,同一高度层,远郊区的平均水平风速大于城区,且受湍流活动影响,城区和远郊区水平风速日变化趋势均为白天小于夜间。春、夏季城区风向受局地山谷风影响显著,以偏西南偏南气流为主,城区和远郊区秋冬季受冷空气活动影响,以西北风为主,且水平风向日变化特征具有季节性差异。远郊区低层大气垂直速度分布特征四季相同,正、负速度出现频率相当,日变化趋势为单峰型;城区冬春季有差异,在390 m高度以下正速度出现频率明显大于负速度,且日变化趋势在四季差异较大。北京城区和郊区风场特征差异与其他特大城市相比无特殊性,主要受大气环流、局地地形、下垫面环境等因素影响。     

Surface Trace Gases at a Rural Site between the Megacities of Beijing and Tianjin

The North China Plain （NCP） has recently faced serious air quality problems as a result of enhanced gas pollutant emissions due to the process of urbanization and rapid economic growth. To explore regional air pollu- tion in the NCP, measurements of surface ozone （O3）, nitrogen oxides （NOx）, and sulfur dioxide （SO2） were car- ried out from May to November 2013 at a rural site （Xianghe） between the twin megacities of Beijing and Tianjin. The highest hourly ozone average was close to 240 ppbv in May, followed by around 160 ppbv in June and July. High ozone episodes were more notable than in 2005 and were mainly associated with air parcels from the city cluster in the hinterland of the polluted NCP to the southwest of the site. For NOx, an important ozone precur- sor, the concentrations ranged from several ppbv to nearly 180 ppbv in the summer and over 400 ppbv in the fall. The occurrence of high NOx concentrations under calm condi- tions indicated that local emissions were dominant in Xianghe. The double-peak diurnal pattern found in NOx concentrations and NO/NOx ratios was probably shaped by local emissions, photochemical removal, and dilution re- sulting from diurnal variations of surface wind speed and the boundary layer height. A pronounced SO2 daytime peak was noted and attributed to downward mixing from an SO2-rich layer above, while the SO2-polluted air mass transported from possible emission sources, which differed between the non-heating （September and October） and heating （November） periods, was thought to be responsible for night-time high concentrations.     

气象条件对梅州城区臭氧浓度的影响研究

利用2014—2017年梅州城区的O3监测数据和相关气象观测资料,对本地区的O3的变化特征及影响O3的气象条件进行了相关分析。分析表明:梅州地区2014—2017年O3超标日数维持稳定水平,O3二级超标日数全部集中在春季和夏季; O3二级超标天数占AQI超标日数的比例快速上升,O3二级超标主要发生在3—8月,最多的是4月,O3是影响梅州市区空气质量重要因素。O3的月平均浓度与同期气温、日照显著正相关,与同期的气压呈显著负相关; O3污染过程中,O3的逐日浓度与同期气温、日照显著正相关,与同期的总云量、低云量、湿度呈显著负相关; O3污染过程中,O3浓度与地面及高空天气形势配置关系密切,O3浓度变化是多种气象要素共同作用的结果。     

江苏省城区VOCs污染特征及其关键活性物种识别

利用2019年8月13日—9月30日江苏省13个设区市离线监测的VOCs数据,对江苏省城区VOCs污染特征及其关键活性组分进行分析研究.结果表明,江苏省逐日VOCs的体积分数范围为8.83×10^-9~45.11×10^-9,表现为烷烃 > 芳香烃 > 烯烃 > 炔烃.江苏省13个设区市VOCs的体积分数为7.85×10^-9~30.52×10^-9,徐州市VOCs最高,这与徐州市监测点位置分布及其工业结构相关.全省13个设区市臭氧浓度处于优、良、轻度污染和中度污染时,VOCs总体积分数分别为14.96×10^-9、17.96×10^-9、25.85×10^-9和25.11×10^-9,臭氧浓度处于污染状态时的VOCs高于优、良状态,且炔烃占比随着臭氧污染程度的加重呈升高趋势,表明现阶段臭氧生成与人类活动关系密切.通过加权的方式筛选出间/对二甲苯、乙烯、甲苯、丙烯、异戊二烯、邻二甲苯等物种,它们是目前对江苏省城区影响程度较大且影响范围较广的关键活性物种.     

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.     

北京地区气溶胶PM2.5粒子浓度的相关因子及其估算模型

文中运用统计分析和气象统计预报的方法 ,使用北京白石桥小区的污染物观测资料和同期北京地区的气象观测资料 ,对影响大气污染的气象因子进行了综合分析 ,并分别建立了气溶胶PM 2 .5粒子浓度与气体污染物、气象要素场的两类统计相关拟合模型。发现气溶胶PM2 .5粒子浓度与气体污染物浓度存在不同程度的相关性 ,且与气象条件亦存在显著的相关关系 ,此类时空变化及其量化估算模型具有一定实际应用价值。通过确定气象要素场和气溶胶浓度的关系可进一步研究不同地区的污染物输送和污染源扩散影响的问题。     

基于敏感源分析的动态大气污染排放方案模拟

选取2014年11月6—11日一次典型污染过程,以北京城区为重点关注的目标区域,基于印痕分析技术判别对该区域影响较大的敏感源区,设计重点区域减排试验和敏感源区逐日动态减排试验,利用区域化学传输模式WRF-Chem进行模拟对比。结果显示:上述两种方案对源强较高的减排当地PM_2.5浓度降低均有明显的改善作用,且在传输作用下会辐射影响到下游地区;但仅就目标区域而言,敏感源区减排方案的减排效率要远远高于重点区域减排方案。为了验证基于敏感源分析的动态减排方法的适用性,进一步开展了不同季节以及不同背景浓度的个例模拟。结果表明:基于敏感源区分析结果制定动态逐日减排措施,可降低削减成本、提高减排效率,以达到最具经济环境效益的减排效果。     

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     

蒙特卡罗不确定性分析在O3模拟中的初步应用

利用蒙特卡罗不确定性分析方法,分析了嵌套网格空气质量模式系统(NAQPMS/IAP)中154个模式输入变量不确定性对臭氧模拟的影响,量化了模式在北京奥运会期间臭氧模拟的不确定性,并确定出了主要不确定性因子。结果表明:(1)在奥运会期间(2008年8月8日～2008年8月24日),北京城区臭氧模拟的平均不确定性为19ppb,不确定性存在明显的日变化特征,白天不确定性大,夜间不确定性小。(2)在白天,北京城区近地层臭氧模拟最重要的不确定性来源是局地前体物排放,其次是NO2光解系数、风向、北京周边前体物排放和垂直扩散系数。另外,地面约150m以上,对臭氧模拟影响最大的不确定性因子是风向和北京周边前体物排放;夜间,北京城区近地层臭氧模拟的最大不确定性来源是局地NOx排放和垂直扩散系数。     

Distribution of surface ozone concentration in the clean areas of china and its possible impact on crop yields

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