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.     

中国东部地区典型臭氧污染过程防控敏感性及减排情景研究

近年来,我国东部地区夏季臭氧污染问题日渐凸显,成为影响空气质量、环境改善的重要因素之一,为量化评估臭氧前体物减排对臭氧污染的影响,本文以2021年6月19—30日中国东部地区臭氧污染过程为例,应用空气质量模型CMAQ-DDM方法与卫星遥感反演算法分析了东部地区臭氧浓度对人为源前体物排放敏感性的响应程度,并对臭氧前体物设置不同削减比例开展减排情景模拟,结果表明:1)2021年6月19—30日中国东部出现了一次长时间区域性臭氧污染过程,大部分城市达轻度至中度污染水平;2)整个污染时段东部地区主要以VOCs(Volatile Organic Compounds,挥发性有机物)控制区或VOCs与NO_x协同控制区为主,模型模拟与卫星反演结果具有较好的一致性,污染过程前段(19—25日)东部地区对VOCs敏感性较高,污染后段(26—30日)大部分地区转为VOCs和NO_x协同控制区,特别是河南、安徽、江苏部分地区,对NO_x敏感性提高较为显著;3)在相同减排比例条件下(VOCs∶NO_x=2∶1),减排幅度越大,臭氧降幅越大,当VOCs削减比例由20％提高到40％时,臭氧浓度降幅由1.7％增大至3.6％;由VOCs和NO_x协同减排(2∶1)过渡为强化NO_x减排(1∶1)的分阶段控制优于单一的减排控制方案,臭氧改善率平均增强0.1％;仅削减高架源NO_x对臭氧降幅不显著。     

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。     

中美大气化学联合考察实验结果的初步分析与比较

根据临安区域本底站观测资料分析结果得出,中国中纬度地区秋、冬季O₃及其前体物NO_x等浓度偏高,可以对农作物和地表生态系统产生影响.观测结果表明:近地层大气O₃浓度主要决定于地面总辐射量控制下的光化学反应过程;O₃的生成受到前体物NO_x的控制,但O₃与NO_x存在着明显的非线性关系.从PEM-WESTA和B的实验及1995年的观测资料表明,O₃的生成效率随着NO_x浓度的增大而减小.尽管O₃的生成速率秋季比冬季的大,但由于秋季较高的NO_x抑制了过氧基的生成,因此冬季O₃的累积量几乎可以和秋季相比拟.在临安观测的NMHC和NO_x的比值比国外同纬度地区测值要大.这说明在临安本底站O₃的光化学生成中,NMHC不是控制物种.从而提示我们,在这些季节临安O₃光化学产物能够被NO_x浓度所控制.中美大气化学联合考察(PEM-WEST-B)实验期间,台湾省的卡盯站SO₂的平均浓度为0.29ppb,O₃的平均浓度为42.2ppb,可以认为此值为低纬度海岛的本底值.1994年PEM-WEST-B实验期间临安站的观测资料和台湾省的卡盯站资料相比,临安站SO₂的浓度约为卡盯站SO₂浓度的50倍左右,从而可以看出人类活动对大气本底的显着影响.     

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.     

武汉市大气污染变化趋势预测

以2014年武汉市大气污染源排放清单为基准,结合《武汉市城市空气质量达标规划（2013-2027年）》研究工作,预测了其实施后在控制"两高"行业新增产能、污染源综合治理、淘汰落后产能、控制机动车保有量等方面对武汉市SO₂、NO_x、PM₁₀、PM_2.5的减排量.利用嵌套网格空气质量预报模式系统（NAQPMS）,模拟分析了《达标规划》大气污染治理重点工程实施的空气质量改善效果.结果表明：《达标规划》实施后,2020年武汉市SO₂、NO₂、PM₁₀和PM_2.5排放量将分别比2014年削减22%~66%、6%~37%、14%~40%和17%~46%;武汉市空气质量有所改善,但NO₂和颗粒物年均浓度仍不能达到环境空气质量二级标准.     

武汉市大气污染源排放清单及分布特征研究

以武汉市为研究区域,基于实地调查获得典型行业污染源活动水平,以大气污染物排放清单编制技术指南为参考,利用排放因子法建立2014年武汉市大气污染源排放清单,并结合经纬度、人口密度分布、土地利用类型、道路长度等数据将排放清单进行了3 km×3 km网格化处理.结果表明,2014年武汉市SO₂、NO_x、PM₁₀、PM_2.5、CO、BC、OC、VOCs和NH₃排放量分别为10.3、17.0、16.3、7.1、63.1、0.6、0.4、19.8和1.6万t.固定燃烧源为SO₂排放的主要来源,其贡献率约64%;移动源为NO_x的主要来源,其贡献率约51%;颗粒物排放主要来源于扬尘源和工艺过程源;CO和VOCs主要来源于工艺过程源,BC和OC排放均以移动源和生物质燃烧源为主,NH₃排放主要来自农业源.污染物排放主要集中在青山区至新洲区一带.     

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.     

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。     

短寿命气候强迫因子的自然源排放及气候反馈:IPCC AR6解读

短寿命气候强迫因子(Short-lived Climate Forcers,SLCFs)对大气污染和气候变化具有重要影响,政府间气候变化专门委员会(IPCC,2021)第六次评估报告(AR6)首次专门设立了关于SLCFs的独立章节,除了对人为源SLCFs评估以外,报告也包含了对于自然源SLCFs及其气候反馈的评估。特别地,在未来气候变暖和人为SLCFs持续减排的背景下,加深对SLCFs的自然源排放及其气候反馈的认识将更为重要。本文从自然源SLCFs排放评估、历史和未来气候情景下的排放变化、SLCFs的气候反馈几个方面解读了AR6中有关的最新结论。未来气候变暖情形下,闪电源NO_x、植被源BVOCs、生物质燃烧排放将会增加,土壤源NO_x、沙尘、海盐颗粒物和二甲基硫(Dimethlysulfide,DMS)对于气候变化的敏感性难以定量。同时,气候变化驱动着SLCFs的排放量、大气含量或寿命的改变,这些过程整体上造成的负反馈参数为-0.20 W/m²/℃(-0.41～+0.01 W/m²/℃),可能从一定程度上缓解气候变暖。     

Stable Carbon Isotope Ratios and the Photochemical Age of Atmospheric Volatile Organic Compounds

Abstract

The dependence of ozone formation on the mixing ratios of volatile organic compounds (VOCs) and nitrogen oxides (NO_x) has been widely studied. In addition to the atmospheric levels of VOCs and NO_x, the extent of photochemical processing of VOCs has a strong impact on ozone levels. Although methods for measuring atmospheric mixing ratios of VOCs and NO_x are well established and results of those measurements are widely available, determination of the extent of photochemical processing of VOCs, known as photochemical age (PCA), is difficult. In this article a recently developed methodology for the determination of PCA for individual compounds based on the change in their stable carbon isotope composition is used to investigate the dependence between ozone and VOC or NO_x mixing ratios at a rural site in Ontario, Canada, during fall and winter. The results show that under these conditions the variability in VOC mixing ratios is predominantly a result of the varying impact of local emissions and not a result of changes in the extent of atmospheric processing. This explains why the mixing ratio of ozone shows no systematic dependence on the mixing ratios of VOCs or NO_x in this environment and at this time of the year.     

Daily, weekly and seasonal relationships among VOCs, NOx x and O3 in a semi-urban area near Barcelona

Daily, weekly, and seasonal patterns of O₃, NOx _x and VOCs and their relationship to meteorological conditions were studied in a semi-urban site near Barcelona by means of five-day long campaigns that included weekend and labor days in December, March, June, and October. The plant protection thresholds for ozone and NO₂ were exceeded, respectively, on all the studied days in summer and on all the studied days. Ozone formation was predominantly local and relied on photochemical processes with VOCs playing a controlling role. Formaldehyde, acetaldehyde, methanol, toluene, isoprene, and acetone (in this order) presented the highest O₃ formation potential during the studied periods. These results highlight the important role in O₃ formation played by VOC species such as acetaldehyde, methanol, and acetone, that all have a significant biogenic component. Thus, these VOCs must be taken into account in the discussion of any ozone abatement strategy.     

Volatile organic compounds at a rural site in western Senegal

The objectives of this study were to identify species and levels of volatile organic compounds (VOCs), and determine their oxidation capacity in the rural atmosphere of western Senegal. A field study was conducted to obtain air samples during September 14 and September 15, 2006 for analyses of VOCs. Methanol, acetone, and acetaldehyde were the most abundant detected chemical species and their maximum mixing ratios reached 6 parts per billion on a volume basis (ppbv). Local emission sources such as firewood and charcoal burning strongly influenced VOC concentrations. The VOC concentrations exhibited little temporal variations due to the low reactivity with hydroxyl radicals, with reactivity values ranging from 0.001 to 2.6 s⁻¹. The conditions in this rural site were rather clean. Low ambient NO _x levels limited ozone production. Nitrogen oxide (NO _x ) levels reached values less than 2 ppbv and maximum VOC/NO _x ratios reached 60 ppbvC/ppbv, with an overall average of 2.4 ± 4.5 ppbvC/ppbv. This indicates that the rural western Senegal region is NO _x limited in terms of oxidant formation potential. Therefore, during the study period photochemical ozone production became limited due to low ambient NO _x levels. The estimated ozone formation reactivity for VOCs was low and ranged between −5.5 mol of ozone/mol of benzaldehyde to 0.6 mol/mol of anthropogenic dienes.     

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.     

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.     

Impact of precursor levels and global warming on peak ozone concentration in the Pearl River Delta Region of China

The relationship between the emission of ozone precursors and the chemical production of tropospheric ozone(O3) in the Pearl River Delta Region(PRD) was studied using numerical simulation.The aim of this study was to examine the volatile organic compound(VOC)-or nitrogen oxide(NOx =NO+NO2)limited conditions at present and when surface temperature is increasing due to global warming,thus to make recommendations for future ozone abatement policies for the PRD region.The model used for this application is the U.S.Environmental Protection Agency’s(EPA’s) third-generation air-quality modeling system;it consists of the mesoscale meteorological model MM5 and the chemical transport model named Community Multi-scale Air Quality(CMAQ).A series of sensitivity tests were conducted to assess the influence of VOC and NOx variations on ozone production.Tropical cyclone was shown to be one of the important synoptic weather patterns leading to ozone pollution.The simulations were based on a tropicalcyclone-related episode that occurred during 14-16 September 2004.The results show that,in the future,the control strategy for emissions should be tightened.To reduce the current level of ozone to meet the Hong Kong Environmental Protection Department(EPD) air-quality objective(hourly average of 120 ppb),emphasis should be put on restricting the increase of NOx emissions.Furthermore,for a wide range of possible changes in precursor emissions,temperature increase will increase the ozone peak in the PRD region;the areas affected by photochemical smog are growing wider,but the locations of the ozone plume are rather invariant.     

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).     

Photochemical characteristics of high and low ozone episodes observed in the Taehwa Forest observatory (TFO) in June 2011 near Seoul South Korea

We present a comprehensive discussion on what cause high ozone episodes at a suburban photochemical observation site of the Seoul Metropolitan Area (population ～23 million). The observational site, Taehwa Research Forest (TRF), is situated ～30 km from the center of Seoul. In June 2011, we observed two very distinctive ozone periods-high ozone (peak up to 120 ppbv) and low ozone (peak up to 60 ppbv) in the mid and early month, respectively. The trace gas measurement dataset, especially CO and NO _X clearly indicate that less anthropogenic influences during the high ozone period. Volatile organic compound (VOC) measurement results show that at the observational site, biogenic VOCs (mostly isoprene) contribute most of chemical reactivity towards OH, although toluene from anthropogenic activities was observed in higher concentrations. Back-trajectory analysis indicates that air-masses from the forest part of Korea Peninsula were dominant influences during the high ozone episode event. On the other hand, Aged air masses from China were the dominant influence during the low ozone episode event. Model calculations conducted using the University of Washington Chemical Mechanism (UWCM) box model, also consistently show that BVOC, especially isoprene photochemistry, can be the significantly contribution to local ozone formation in the given photochemical environments of TRF. These research results strongly suggest that ozone control strategy in the Eastern Asian megacities, mostly situated in surrounding forest areas should be based on the comprehensive scientific understanding in BVOC photochemistry and interplays between anthropogenic and biogenic interactions.     

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.     

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.