基于模式分析一次沙尘暴过程中沙尘表面非均相化学过程对中国地区污染物浓度的影响

利用戈达德对地观测系统（GEOS）提供的再分析气象场GEOS-5驱动的GEOS-Chem模式,模拟中国地区2009年4月22~29日沙尘暴期间沙尘气溶胶表面非均相化学过程对我国污染物的影响。模拟结果表明,沙尘暴期间,全国平均沙尘硝酸盐和沙尘硫酸盐浓度分别为0.2 μg m-3和0.4 μg m-3,占总硝酸盐（非沙尘硝酸盐与沙尘硝酸盐之和）和总硫酸盐（非沙尘硫酸盐与沙尘硫酸盐之和）的24%和10%。我国西部地区沙尘硝酸盐占比（ > 80%）要大于其他地区,而西部地区的沙尘硫酸盐占比则要小于下游地区。考虑非均相化学反应后,沙尘暴期间,全国平均的二氧化硫（SO₂）、硝酸（HNO₃）、臭氧（O₃）、非沙尘硫酸盐、总硫酸盐、非沙尘硝酸盐、总硝酸盐、NH₃、总铵盐浓度变化量分别为-7%、-15%、-2%、-8%、3%、-2%、14%、21%、-5%。     

东亚地区沙尘气溶胶影响硫酸盐形成的模式评估

利用STEM-II三维区域大气化学模式,耦合沙尘气溶胶表面相过程,研究了1994年3月1日至14日间东亚地区沙尘气溶胶对硫酸盐形成的影响。结果表明,SO2气体在沙尘气溶胶表面上进行的非均相氧化过程是硫酸盐形成的一条重要途径,由这条途径提供的硫酸盐占其总浓度的20%～50%。 并发现在模拟时段,沙尘暴过程主要影响沙尘源地下游的中国东部地区硫酸盐的分布,使得那里的硫酸盐浓度增加60%以上。     

北京春季沙尘和霾期间气溶胶的对比模拟研究

利用气象模式WRF驱动区域空气质量模式RAQMS,模拟研究了2014年北京地区春季颗粒物及气溶胶化学组分的时空变化,对比分析了沙尘期（3月17日、29日）和霾期（3月25～27日）的天气形势、气象要素和气溶胶化学组分特征,比较了沙尘和人为气溶胶表面非均相化学反应对大气化学成分的影响及相对贡献。结果显示,模式对于气象要素、PM2.5、PM10及其化学组分具有较好的模拟能力,考虑了气溶胶表面非均相化学反应后明显提高了模式对PM2.5及气溶胶化学组分模拟的准确性。沙尘期间,沙尘对PM10质量浓度贡献占主导地位（50.7%）,对PM2.5的贡献与有机气溶胶（OM）和人为排放的一次颗粒物（PPM）相当;霾期间,硝酸盐NO₃?（25.6%）和OM（23.6%）对PM2.5的贡献最大,在PM10中NO₃?、PPM和OM的贡献相当。沙尘期,粗粒子明显增加,在PM10中所占比例与细粒子相当,为45.5%;霾期,细粒子占主导地位,占PM10质量浓度的85.6%。非均相化学反应使沙尘期间硫酸盐（SO₄2–）和NO₃–浓度分别增加16.9%和83.8%,使霾期间的SO₄2?和NO₃–浓度分别增加14.5%和45.0%。2014年3月,非均相化学反应使北京月均SO₂、NO₂、O₃、SO₄2?、NH₄+和NO₃?的浓度分别变化了?2.5%、?5.7%、?3.4%、11.7%、18.6%和58.5%,本文结果表明非均相化学反应对二次无机气溶胶的生成有重要贡献。     

碘代异丙烷在黑碳表面的吸附研究

黑碳气溶胶由于其对大气辐射平衡和气候的影响而受到高度重视,碘化学则是大气化学中十分重要的研究领域。然而对于卤素化合物尤其含碘化合物与黑碳气溶胶表面相互作用的研究还少有报道。文中首次研究了在298K下,碘氧自由基(IO)重要源之一的碘代异丙烷(i-C3H7I)在黑碳表面的吸附,黑碳样品使用DegussaFW2(一种含有氧化态的无定形黑碳)。实验发现碘代异丙烷与黑碳表面发生相互作用,使黑碳表面逐渐被钝化,并且其吸附系数(γ)与暴露时间相关。实验测得初始吸附系数(γ0)值为(9.5±3.8)×10-2。所报道的初始吸附系数γ0可以提供一个上限值,实验结果表明在真实大气环境下,i-C3H7I在黑碳气溶胶表面的非均相消耗可能是十分重要的,也许会对i-C3H7I在真实大气中的浓度有一定影响。并且研究结果对进一步研究i-C3H7I与黑碳气溶胶相互作用对大气辐射平衡、黑碳气溶胶非均相化学作用和云雾降水凝结核(CCN)形成的影响均有十分重要的意义,研究结果也为评估i-C3H7I与碳质气溶胶非均相相互作用对大气环境的影响和深入的模式研究提供了基本参数。     

春季中国东部气溶胶化学组成及其分布的模拟研究

本文利用区域空气质量模式RAQMS（Regional Air Quality Model System）,对2009年春季中国东部气溶胶主要化学成分及其分布进行了模拟研究。与泰山站观测资料的对比结果显示,模式能比较合理地反映气溶胶浓度的逐日变化特征。整体上,模式对无机盐气溶胶的模拟好,分别高估和低估黑碳和有机碳气溶胶浓度,其原因与排放源、二次有机气溶胶化学机制和模式分辨率的不确定性有关。模拟结果显示,春季气溶胶浓度高值主要集中于华北、四川东部、长江中下游等地区。受东南亚生物质燃烧和大气输送的影响,中国的云南和广西等地区有机碳浓度高于中国其他地区。中国西北部沙尘浓度较高,而且向东输送并影响到中国东部和南方部分地区。中国东部的华北、四川东部、长江中下游等地PM_2.5（空气动力学直径在2.5微米以下的颗粒物）污染严重,4月平均PM_2.5浓度超过了我国日平均PM_2.5浓度限值。中国东部泰山站的观测和模拟结果都显示近地面硝酸盐浓度超过硫酸盐,中国北部对流层中硝酸盐的柱含量也大于硫酸盐,而在中国南部则相反,这一方面与春季中国云量 南多北少的分布特征以及云内液相化学反应有关,另一方面也与南北温差对气溶胶形成的影响有关。就整个中国东部而言,虽然硫酸盐的柱含量（46 Gg）仍大于硝酸盐（42 Gg）,但比较接近,反映出我国氮氧化物排放迅速增加的趋势。春季中国地区对流层中PM₁₀（空气动力学直径在10微米以下的颗粒物）及其化学成分柱含量分别为:990.8 Gg（PM₁₀）,52.6 Gg（硫酸盐）,48.2 Gg（硝酸盐）,32.1 Gg（铵盐）,22.9 Gg（黑碳）和74.1 Gg（有机碳）,有机碳（OC）中一次有机碳（POC）和二次有机碳（SOC）分别占60%和40%,中国东部PM₁₀中人为气溶胶和沙尘分别占30%和70%,反映了春季沙尘对我国大气气溶胶的重要贡献。     

近10年东亚沙尘气溶胶时空分布与起尘通量的数值研究

利用一个耦合了沙尘模型的区域气候模式RegCM3和NCEP再分析资料,对近10年(2000-2009年)东亚地区沙尘气溶胶(直径≤20μm)时空分布特征和起尘通量进行了数值模拟。结果表明,(1)耦合模式能较好地模拟东亚地区沙尘气溶胶的时空分布特点。东亚地区沙尘气溶胶光学厚度、柱含量高值区主要位于塔克拉玛干沙漠和巴丹吉林沙漠。沙尘气溶胶柱含量的季节变化特征明显,春季最大,冬季次之,秋季最小。东亚地区110°E以东,沙尘主要以700hPa高度为中心向东传输。(2)东亚地区起沙源区主要位于塔克拉玛干沙漠、巴丹吉林沙漠、藏北沙漠化地区及蒙古国西南部,起沙强度存在明显的季节变化。2000-2009年东亚地区年平均起沙通量为1015.34mg.m-2.d-1,其中62.4%和2.3%分别通过干、湿过程重新沉降在东亚地区,其余35.3%被净释放进入大气或进行远距离传输。     

海盐气溶胶影响酸碱气体及无机盐气溶胶的敏感性试验

利用热力学平衡模式ISORROPIA及与之耦合的气相化学模式,通过两类敏感性试验,探讨了海盐气溶胶、相对湿度、温度对3种无机盐（硫酸盐、硝酸盐、铵盐,包括液态和固态）和3种酸碱气体（氨气、气态硝酸、氯化氢）浓度的影响,以及不同海盐气溶胶浓度对热力学平衡的影响。试验结果表明,海盐浓度相对较低、相对湿度达到0．4～0．5以上、温度在-10～15℃之间时对各物种的平衡浓度影响比较显著。温度升高抑制硝酸盐、铵盐的生成,同时引起气态硝酸、氨气和氯化氢浓度的增加。而湿度升高时对硝酸盐、铵盐的生成有促进作用,反而造成气态硝酸、氨气和氯化氢浓度的降低。海盐气溶胶、相对湿度及温度的变化对硫酸盐气溶胶没有影响。在热力学平衡中如果考虑海盐气溶胶（主要成分NaGl）的作用会使得硝酸盐气溶胶、氨气浓度增加,而硝酸气体、铵盐气溶胶浓度减小,其中硝酸盐和气态硝酸的改变最为明显。由于海盐气溶胶和硫酸、硝酸的反应,产生了氯化氢气体,造成海盐气溶胶的氯亏损现象。     

东亚地区春季二氧化硫的输送与转化过程研究I.模式及其验证

结合新近评估的东亚地区污染源资料,作者利用一个耦合的区域化学输送模式系统以探讨东亚地区春季期间气象过程、气相与液相化学过程、非均相化学过程、气溶胶过程和干湿沉降过程对二氧化硫输送及转化过程的影响,并研究二氧化硫和硫酸盐气溶胶的空间分布及变化特征.模拟的二氧化硫和硫酸盐气溶胶的浓度值与2001年春季飞机和地面获取的观测值进行了比较.比较结果显示,模拟值与观测值具有很好的一致性,模式系统很好地反映了二氧化硫和硫酸盐气溶胶的分布特征和变化规律,再现了许多观测到的重要特征,为进一步分析模拟结果奠定了基础.     

新疆和田市沙尘气溶胶浓度及粒径分布特征研究

沙尘气溶胶不仅影响天气和气候,而且对海洋生态及全球物质循环具有重要的作用.塔克拉玛干沙漠作为我国和东亚地区重要的沙尘气溶胶源区,其西南缘和田市沙尘气溶胶浓度及粒径分布特征尚不明确,将不利于该区域沙尘气溶胶远距离输送和沉降的机理研究.因此,本文利用粒子分级采样仪,通过对和田市不同天气(晴天、浮尘、扬沙天气)下沙尘气溶胶浓...     

Chemical characterization of submicron particles during typical air pollution episodes in spring over Beijing

2012年春季北京经历了罕见的连续污染过程,本研究着眼于霾及沙尘污染事件,对比探讨了两典型污染事件中亚微米细颗粒物(PM_1)化学组分的差异。结果表明:霾事件中,PM_1硝酸盐增长最为明显且所占比重最大,硝酸盐在PM_1浓度迅速增加,其中1质量浓度的平均占比为32.2%,最大可达42%,这与其它季节霾污染特性显著不同,二次无机气溶胶(硝酸盐,硫酸盐,铵盐)增长明显,平均质量浓度为55.1±23.8μg m~(-3),PM_1有机气溶胶所占比重1的质量贡献为66.5%。沙尘污染事件的化学组分特性与霾事件显著不同,最大,PM_1浓度为8.9±5.4μg m~(-3),二次无机气溶胶质量浓度较低,且仅1平均质量贡献为64.0%,平均占PM_1气污染控制策略的制定需依据气溶胶的特点及形成机理有1质量浓度的34.0%。本研究表明,空针对性进行。     

对流层光化学过程中的气粒转化研究

在MM5和RADM耦合的基础上，考虑了NH3的源排放，获得了NH3的时空分布、演变特征；在此基础上，讨论了气体向粒子的转化，结果表明:干气溶胶总量分布与大气中H2SO4、NH3的浓度分布有非常好的对应，富氨环境条件下，产生干气溶胶的多少是由H2SO4浓度决定的；气溶胶中的含水量与干气溶胶的浓度分布没有太多的联系，主要取决于大气中相对湿度的大小。     

Modeling Study of the Impact of Heterogeneous Reactions on Dust Surfaces on Aerosol Optical Depth and Direct Radiative Forcing over East Asia in Springtime

The spatial distributions and interannual variations of aerosol concentrations,aerosol optical depth(AOD) ,aerosol direct radiative forcings,and their responses to heterogeneous reactions on dust surfaces over East Asia in March 2006-10 were investigated by utilizing a regional coupled climate-chemistry/aerosol model. Anthropogenic aerosol concentrations(inorganic+carbonaceous) were higher in March 2006 and 2008,whereas soil dust reached its highest levels in March 2006 and 2010,resulting in stronger aerosol radiative forcings in these periods.The domain and five-year(2006-10) monthly mean concentrations of anthropogenic and dust aerosols,AOD,and radiative forcings at the surface(SURF) and at the top of the atmosphere(TOA) in March were 2.4μg m-3,13.1μg m-3,0.18,-19.0 W m-2,and-7.4 W m-2,respectively.Heterogeneous reactions led to an increase of total inorganic aerosol concentration;however,the ambient inorganic aerosol concentration decreased,resulting in a smaller AOD and weaker aerosol radiative forcings.In March 2006 and 2010,the changes in ambient inorganic aerosols,AOD,and aerosol radiative forcings were more evident.In terms of the domain and five-year averages,the total inorganic aerosol concentrations increased by 13.7%(0.17μg m-3) due to heterogeneous reactions,but the ambient inorganic aerosol concentrations were reduced by 10.5%(0.13μg m-3) .As a result,the changes in AOD,SURF and TOA radiative forcings were estimated to be-3.9%(-0.007) ,-1.7%(0.34 W m-2) ,and-4.3%(0.34 W m-2) ,respectively,in March over East Asia.     

Influence of Atmospheric Particulate Matter on Ozone in Nanjing,China:Observational Study and Mechanistic Analysis

Particulate matter with diameters of 2.5 μm or smaller(PM_(2.5)) and ozone(O_3) are major pollutants in the urban atmosphere. PM_(2.5) can affect O_3 by altering the photolysis rate and heterogeneous reactions. However, these two processes and their relative importance remain uncertain. In this paper, with Nanjing in China as the target city, we investigate the characteristics and mechanism of interactions between particles and O_3 based on ground observations and numerical modeling.In 2008, the average concentrations of PM_(2.5) and O_3 at Caochangmen station are 64.6 ± 47.4 μg m~(-3) and 24.6 ± 22.8 ppb,respectively, while at Pukou station they are 94.1 ± 63.4 μg m~(-3) and 16.9 ± 14.9 ppb. The correlation coefficient between PM_(2.5) and O_3 is -0.46. In order to understand the reaction between PM_(2.5) and O_3, we construct a box model, in which an aerosol optical property model, ultraviolet radiation model, gas phase chemistry model, and heterogeneous chemistry model,are coupled. The model is employed to investigate the relative contribution of the aforementioned two processes, which vary under different particle concentrations, scattering capability and VOCs/NOxratios(VOCs: volatile organic compounds;NOx: nitric oxide and nitrogen dioxide). Generally, photolysis rate effect can cause a greater O_3 reduction when the particle concentrations are higher, while heterogeneous reactions dominate O_3 reduction with low-level particle concentrations.Moreover, in typical VOC-sensitive regions, O_3 can even be increased by heterogeneous reactions. In Nanjing, both processes lead to O_3 reduction, and photolysis rate effect is dominant. Our study underscores the importance of photolysis rate effect and heterogeneous reactions for O_3, and such interaction processes should be fully considered in future atmospheric chemistry modeling.     

平流层臭氧非线性响应的机理研究

完善了王革丽和杨培才(2007)建立的平流层下部臭氧异相光化学反应箱式模式,在原有模式基础上加入溴族,研究了平流层下部臭氧对硫酸气溶胶表面积浓度与氯化物、溴化物以及氮氧化物的排放强度变化的非线性响应,理解平流层臭氧对人类活动的依赖性.结果表明,当氯化物排放强度偏离当前水平时,气溶胶可以通过与溴化物、氯化物、氮氧化物之间的相互作用,干预光化系统的非线性行为,改变系统在参数空间中的拓扑结构.     

Numerical Investigation of the Influence of Mineral Dust on the Tropospheric Chemistry of East Asia

An investigation of the influence of mineral dust ontrace gas cycles in the troposphere is carried out inthis study. A 3D regional scale atmospheric chemistrymodel (STEM-III) which includes aerosol processes isused for the numerical simulations for May 1987.Heterogeneous interactions between gaseous species(SO₂, N₂O₅, HNO₃, HO₂andH₂O₂) and the dust particles are considered.Emissions of dust behind convective cold fronts aremodeled. The transport and distribution of mineraldust predicted from the model is compared withsatellite measurements (aerosol index from TOMS). Themodel is shown to capture the synoptic variability inthe observed aerosol index. Calculations show twomajor dust events in May 1987, during which thedust levels close to the source reach more than500 g/m³. The transport of dust is mostlyrestricted towards the north, with the net continentaloutflow of 6 Tg for the entire month. Results showthat the presence of mineral aerosol can greatlyimpact sulfate and nitrate distributions. Averagedover the month of May, the presence of dust isestimated to increase particulate sulfate and nitratelevels in east Asia by 40%. Furthermore, the sulfateand nitrate on the dust particles are predicted to beassociated with the coarse mode (3–5 m particlediameter), consistent with observations over Japan.The influence of mineral dust on the photochemicaloxidant cycle is also investigated. For the entiremonth, a5–10% decrease in boundary layer ozone ispredicted by the model closer to regions of higherdust levels. The ratio of nitric acid to NO_x overmarine regions is reduced by a factor between 1 and 2in the boundary layer to more than 2 in the freetroposphere as a result of aerosol processes.     

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.     

The impact of high altitude aircraft on the ozone layer in the stratosphere

The paper discusses the potential effects on the ozone layer of gases released by the engines of proposed high altitude supersonic aircraft. The major problem arises from the emissions of nitrogen oxides which have the potential to destroy significant quantities of ozone in the stratosphere. The magnitude of the perturbation is highly dependent on the cruise altitude of the aircraft. Furthermore, the depletion of ozone is substantially reduced when heterogeneous conversion of nitrogen oxides into nitric acid on sulfate aerosol particles is taken into account in the calculation. The sensitivity of the aerosol load on stratospheric ozone is investigated. First, the model indicates that the aerosol load induced by the SO₂ released by aircraft is increased by about 10–20% above the background aerosols at mid-high latitude of the Northern Hemisphere at 15 km for the NASA emission scenario A (the NASA emission scenarios are explained in Tables I to III). This increase in aerosol has small effects on stratospheric ozone. Second, when the aerosol load is increased following a volcanic eruption similar to the eruption of El Chichon (Mexico, April 1982), the ozone column in spring increases by as much as 9% in response to the injection of NO _x from the aircraft with the NASA emission scenario A. Finally, the modeled suggests that significant ozone depletion could result from the formation of additional polar stratospheric clouds produced by the injection of H₂O and HNO₃ by the aircraft engines.     

Simulated Impacts of Sulfate and Nitrate Aerosol Formation on Surface-Layer Ozone Concentrations in China

The authors quantify the impacts of sulfate and nitrate aerosol formation on surface-layer 03 concentrations over China using the one-way nested-grid capa- bility of the global three-dimensional Goddard Earth Ob- serving System chemical transport model （GEOS-Chem）. Chemical reactions associated with sulfate formation are simulated to generally increase 03 concentrations in China. Over the North China Plain （NCP） and the Si- chuan Basin （SCB）, where simulated sulfate concentra- tions are the largest, ozone concentrations show maximum increases in spring by 1.8 ppbv （3.2%） in the NCP and by 2.6 ppbv （3.7%） in the SCB. On the contrary, nitrate formation is simulated to reduce 03 concentrations by up to 1.0 ppbv in eastern China, with the largest reduc- tions of 1.0 ppbv （1.4%） in summer over the NCE Ac- counting for the formation of both sulfate and nitrate, the surface-layer O3 concentrations over a large fraction of eastern China are simulated to increase in winter, spring, and autumn, dominated by the impact of sulfate forma- tion, but to decrease in summer because of the dominant contribution from nitrate formation.