Modelling the formation of H2SO4–H2O particles in rural, urban and marine conditions

The factors which affect the formation of new sulphuric acid particles in different atmospheric conditions are investigated. An atmospheric chemistry gas phase box model coupled to a three mode integral aerosol dynamics model is used. The simulations show the dependence of the concentration of nucleation mode particles on initial pre-existing particles, the intensity of UV radiation, the emissions of dimethylsulphide (DMS) and the ratio of emissions of hydrocarbons (HC) and NO_x present in the atmosphere. Eight different basic cases are simulated in urban, rural and marine conditions. The effects of pre-existing particles as a sink of sulphuric acid are clearly seen. The increased UV radiation is also seen to enhance particle formation via sulphuric acid route significantly.     

Characteristics of cirrus clouds and its radiative properties based on lidar observation over Chung-Li, Taiwan

In this paper, characterization of cirrus clouds are made by using data from ground based polarization lidar and radiosonde measurements over Chung-Li (24.58°N, 121.10°E), Taiwan for a period of 1999–2006. During this period, the occurrence of cirrus clouds is about 37% of the total measurement nights over the lidar site. Analysis of the measurement gives the statistical characteristics about the macrophysical properties such as occurrence height, ambient temperature, and its geometrical thickness while the microphysical properties are interpreted in terms of extinction coefficient, optical depth, effective lidar ratio and depolarization ratio. The effective lidar ratio has been retrieved by using the simulation technique of backscattered lidar signals. The effect of multiple scattering has been taken into the account by a model calculation. Summer (Jun–Aug) shows the maximum appearances of cirrus due to its formation mechanism. It is shown that tropopause cirrus clouds may occur with a probability of about 24%. These clouds are usually optically thin and having laminar in structure with some cases resembling the characteristics similar to that of polar stratospheric clouds (PSCs). The radiative properties of the cirrus clouds are also discussed in detail by the empirical equations with results show a positive feedback on any climate change.     

利用HALOE资料分析中层大气中水汽和甲烷的分布特征

采用SLIMCAT化学传输模式以及再分析资料,对比分析了1997和2011年北极地区平流层臭氧异常偏低事件及其成因。结果表明,1997和2011年3月北极地区大气臭氧柱总量（TCO）异常值都达到了约-80 DU,并且在30-200 hPa（中下平流层）区域的大气臭氧柱总量异常约占整层大气臭氧柱总量异常的80%。分析表明发生在这两年的极端臭氧偏低事件均可能是由于上一年冬季的拉尼娜事件导致上传的行星波减少,使得北极极涡加强,平流层温度异常偏低,生成了更多极地云,引起更强的臭氧化学损耗导致的。对比这两年的大气臭氧柱总量变化发现,2011年的柱总量减少得更快。2011年北极地区上对流层下平流层（UTLS）区域臭氧下降要明显强于1997年,其主要原因应该是2010-2011冬季的拉尼娜活动更强,北太平洋海温更高,进一步减弱阿留申低压和平流层波活动。这导致2011年极涡温度异常偏低更强烈,形成了更多的极地平流层云甚至出现了第二类极地平流层云,最终加速该年春季的臭氧化学损耗引起的。     

Behaviour of H2O2, NH3, and black carbon in mixed-phase clouds during CIME

We investigated the partitioning of trace substances during the phase transition from supercooled to mixed-phase cloud induced by artificial seeding. Simultaneous determination of the concentrations of H₂O₂, NH₃ and black carbon (BC) in both condensed and interstitial phases with high time resolution showed that the three species undergo different behaviour in the presence of a mixture of ice crystals and supercooled droplets. Both H₂O₂ and NH₃ are efficiently scavenged by growing ice crystals, whereas BC stayed predominantly in the interstitial phase. In addition, the scavenging of H₂O₂ is driven by co-condensation with water vapour onto ice crystals while NH₃ uptake into the ice phase is more efficient than co-condensation alone. The high solubility of NH₄⁺ in the ice could explain this result. Finally, it appears that the H₂O₂–SO₂ reaction is very slow in the ice phase with respect to the liquid phase. Our results are directly applicable for clouds undergoing limited riming.     

CH4和N2O的辐射强迫与全球增温潜能

CH₄和N₂O作为主要温室气体,自工业革命以来排放量急剧增加,已经被列入《京都议定书》要求控制它们的排放。本文利用高光谱分辨率的辐射传输模式,计算了CH₄、N₂O在晴空大气和有云大气条件下的瞬时辐射效率和平流层调整的辐射效率,以及它们的全球增温潜能(GWP)和全球温变潜能(GTP),并根据模式结果拟合了CH₄和N₂O的辐射强迫的简单计算公式。本文的研究表明:CH₄和N₂O在有云大气下的平流层调整的辐射效率分别为4.142×10-4 W m-2 ppb-1和3.125×10-3 W m-2 ppb-1 (1ppb=10-9),经大气寿命调整后的辐射效率分别为3.732×10-4 W m-2 ppb-1和2.987×10-3 W m-2 ppb-1,与IPCC(2007)的相应结果高度一致。CH₄和N₂O 100年的全球增温潜能GWP分别为16和266;100年的脉冲排放的全球温变潜能GTPP分别为0.24和233;持续排放的全球温变潜能GTPS分别为18和268。它们在未来全球变暖和气候变化中,影响仅次于CO₂,仍然起着非常关键的作用。     

H2O/CO2污染对煤油燃料超声速燃烧影响数值研究

在纯净空气与H₂O/ CO₂污染空气来流对比试验结果基础上,采用数值计算方法和化学动力学方法,研究了H₂O和CO₂污染组分对煤油燃料超声速燃烧的影响,获得了试验手段难以得到的燃烧室流场参数和性能数据。完成了相应的煤油燃料超声速燃烧室二维数值计算,其中匹配了进口总温、总压、马赫数、氧气摩尔分数和工作当量油气比。将数值计算结果与相应试验测量值进行了对比分析,并结合燃烧室流场数据、性能参数分析了H₂O和CO₂污染的动力学影响、以及对燃烧室性能的影响。研究表明:(1)数值计算结果与实验测量值总体上吻合,两种手段均体现了纯净空气来流时不同煤油当量油气比的燃烧室性能,并反映了一致的“污染效应”影响趋势;(2) H₂O污染、H₂O+ CO₂污染的存在降低了煤油燃料超声速燃烧室性能,体现在燃烧诱导压升、燃烧效率、流向冲量增量的下降,而且随着污染组分含量的增加,燃烧室性能下降越加显著。      

H2释放扰动电离层的数值模拟

由于电离层中分子性离子与电子的复合要比氧离子与电子的复合快得多,因此H₂在电离层高度释放可有效地引起电子的消耗。本文基于一个包括中性气体扩散方程和离子化学反应方程的二维动力学模型,对H₂在电离层高度释放过程进行了数值模拟研究,并分析了不同释放条件下的电子扰动特性。结果表明:1)500 mol H₂释放后,迅速向周围空间扩散,释放中心处的电子密度30 s内下降了近4%,F₂层临界频率下降了1%左右;2)在不同高度处释放H₂时,最大的电子密度相对变化率并不是在峰值高度附近处释放时出现的;3)释放化学物质的量越多,电子密度的扰动幅度也越大,但两者之间并不存在线性关系;4)相同量的H₂在电离层峰值高度处释放,白天的电子密度扰动幅度要大于夜间的扰动幅度。     

地对空微波遥感温度、水汽廓线的联合求解

本文讨论了地对空微波遥感时5毫米吸收带各通道间的相关性,对各种地对空温度反演方法进行了比较。并应用蒙特卡洛法和统计控制法进行了温度、水汽的联合反演,挑选了最佳反演通道,取得了较为满意的数值结果。     

氟利昂C2Cl2F4分子的光谱及解离动力学研究

采用密度泛函B3LYP理论对氟利昂C₂Cl₂F₄ (F-114)在6-31G++(d,p)基组水平上进行分子结构优化、红外光谱计算,理论计算所得结果与实验结果基本吻合.此外又通过从头算CIS方法计算了C₂Cl₂F₄及其离子的低激发态,将所得分子低激发态的键长、键角及二面角等参数进行了对比分析,并得到了C₂Cl₂F₄分子的UV-Vis光谱和分子前线轨道,最后对C₂Cl₂F₄⁺离子的低激发态光解离动力学进行了分析.     

Development of an online analyzer of atmospheric H2O2 and several organic hydroperoxides for field campaigns

An online automated instrument was developed for atmospheric measurements of hydroperoxides with separation and quantification of H₂O₂ and several organic hydroperoxides. Samples were trapped in aqueous solutions in a scrubbing glass coil. Analyses were performed on an HPLC column followed by para-hydroxyphenylacetic acid (POPHA) acetic acid and peroxidase derivatization and fluorescence detection. Analytical and sampling tests were performed on different parameters to obtain optimum signal-to-noise ratios, high resolution and collection efficiencies higher than 95% for H₂O₂ and organic hydroperoxides. The obtained performances show large improvements compared to previous studies. The sampling and analytical devices can be coupled providing an online analyzer. The device was used during two field campaigns in the Marseilles area in June 2001 (offline analyzer) and in July 2002 (online analyzer) at rural sites at low and high altitudes, respectively, during the ESCOMPTE and BOND campaigns. During the ESCOMPTE campaign, H₂O₂ was detected occasionally, and no organic hydroperoxides was observed. During the BOND campaign, substantial amounts of H₂O₂ and 1−HEHP+MHP were often detected, and two other organic hydroperoxides were occasionally detected. These observations are discussed.     

厌氧条件下土壤反硝化气体(N2、N2O、NO)和CO2排放——氦环境培养—气体同步直接测定法的应用初探

反硝化过程是维系闭合氮循环所必需的氮素形态转化环节。土壤反硝化过程速率及产物比的直接测定是研究氮循环过程机理的基础,但却是一个难题。为解决此难题,德国卡尔斯鲁厄技术研究所与中国科学院大气物理研究所最近合作新建了一套通过氦环境培养-气体同步直接测定土壤反硝化气体--氮气（N2）、氧化亚氮（N2O）、一氧化氮（NO）和二氧化碳（CO2）排放的系统和与之配套的三阶段培养方法。为检验该新建系统和配套方法测定土壤反硝化过程的准确性和可靠性,以华北地区广泛分布的盐碱地农田土壤（采自山西运城）为研究对象开展实验室培养试验,在初始可溶性有机碳（DOC）供应比较充足约300 mgC kg–1干土（d.s.）的条件下,测试了不同初始土壤硝态氮含量水平（10、100 mgN kg–1d.s.左右,分别表示为10N和100N）的反硝化气体和CO2排放过程。结果显示：100N的反硝化速率（定义为N2、N2O 和NO 排放速率之和）显著高于10N 处理（统计检验显著水平p＜0.01）;两个处理的反硝化产物均以N2为主（质量比分别占77%和75%）,产物的NO/N2O摩尔比分别为1.2和1.5,N2O/N2摩尔比均为0.19;土壤反硝化气体动态排放速率及相关指标的测定结果表明,培养土壤中消失的硝态氮被回收81%～87%,培养前后的氮平衡率达92%～95%。因此,该新建方法测定土壤反硝化速率和产物比的结果具有很好的可靠性,为定量研究土壤反硝化过程提供了有效的直接测定手段。研究中检测到的土壤反硝化产物NO/N2O摩尔比大于1,不同于以往用液体培养基纯培养反硝化细菌得出的NO/N2O摩尔比远小于1的结论。这意味着,不能用NO/N2O摩尔比小于1与否来推断土壤排放的N2O和NO是主要来源于反硝化作用还是硝化作用。     

[Bmin][BF4]+AMP复合溶液捕集温室气体CO2

采用基于离子液体[Bmin][BF₄]+AMP作为捕集CO₂的复合溶液,在膜吸收-热再生循环装置上,研究了该复合溶液捕集CO₂的过程和传质性能;通过阻力层传质模型,比较了预测值与实验值.结果表明：在相同条件和较高负载下,复合溶液具有较高的传递推动力和更高的传质系数;模型预测值和实验值符合较好,平均误差为12.8%.实验证明复合溶液的传质性能优于单一溶液.