Mechanism development and modelling of tropospheric multiphase halogen chemistry: The CAPRAM Halogen Module 2.0 (HM2)

A new detailed multiphase halogen mechanism, the CAPRAM Halogen Module 2.0 (HM2), has been developed and coupled to the multiphase chemistry mechanism RACM-MIM2ext/CAPRAM 3.0n. The overall mechanism comprises 1,705 reactions including 595 reactions of the HM2. Halogen chemistry box model studies have been, for the first time, performed with a non-permanent cloud scenario for pristine open ocean regions in mid-latitudes. Moreover, detailed time-resolved reaction flux analysis has been used to investigate the multiphase halogen reaction cycles in more detail. Clouds significantly change the multiphase halogen chemical system and new reaction cycles are proposed for in-cloud conditions. While most gas phase concentrations are decreased for chlorine and iodine species, they are increased for bromine. Flux analyses determined the relative contributions of the methylene dihalides CH₂IX (X = Cl, Br, I) as the main I atom source with a contribution of about 80 % to the total iodocarbon sources. Furthermore, HOI was confirmed to be important for chlorine activation. It is shown that 25 % of the ozone loss can be attributed to halogens. VOC oxidation by halogens is important as halogens account for about 20 % of the methane oxidation and up to 80 % of the oxidation of other VOCs. In other cases, enhanced VOC and VOC oxidation product concentration levels were found. For example, 15 % of the methyl peroxyl radicals are formed after the reaction of chlorine atoms with methane or methyl hydroperoxide. In the aqueous phase, changes in the oxidation of organics do only occur for highly oxidised organics without a C-H bond. For example, over 80 % of oxalic acid are oxidised by electron transfer with Cl₂ ^? in deliquescent particles during non-cloud periods.     

Modelling the multiphase near-surface chemistry related to ozone depletions in polar spring

Near-total depletions of ozone have been observed in the Arctic spring since the mid 1980s. The autocatalytic reaction cycles involving reactive halogens are now recognized to be of main importance for ozone depletion events in the polar boundary layer. We present sensitivity studies using the model MISTRA in the box-model mode on the influence of chemical species on these ozone depletion processes. In order to test the sensitivity of the chemistry under polar conditions, we compared base runs undergoing fluxes of either Br₂, BrCl, or Cl₂ to induce ozone depletions, with similar runs including a modification of the chemical conditions. The role of HCHO, H₂O₂, DMS, Cl₂, C₂H₆, HONO, NO₂, and RONO₂ was investigated. Cases with elevated mixing ratios of HCHO, H₂O₂, DMS, Cl₂, and HONO induced a shift in bromine speciation from Br / BrO to HOBr/HBr, while high mixing ratios of C₂H₆ induced a shift from HOBr/HBr to Br/BrO. The shifts from Br/BrO to HOBr/HBr accelerated the aerosol debromination, but also increased the total amount of deposited bromine at the surface (mainly via increased deposition of HOBr). For all NO_y species studied (HONO, NO₂, RONO₂) the chemistry is characterized by an increased bromine deposition on snow reducing the amount of reactive bromine in the air. Ozone is less depleted under conditions of high mixing ratios of NO_x. The production of HNO₃ led to the acid displacement of HCl, and the release of chlorine out of salt aerosol (Cl₂ or BrCl) increased.     

Multiphase chemistry and acidity of clouds at Kleiner Feldberg

The chemistry of cloud multiphase systems was studied within the Kleiner Feldberg Cloud Experiment 1990. The clouds encountered during this experimental campaign could be divided into two categories according to the origin of air masses in which the clouds formed. From the chemical point of view, clouds passing the sampling site during the first period of the campaign (26 October-4 November) were characterized by lower pollutant loading and higher pH, as compared to clouds during the final period of the experimental campaign (10–13 November). The study of multiphase partitioning of the main chemical constituents of the cloud systems and of atmospheric acidity within the multiphase systems themselves (gas + interstitial aerosol + liquid droplets) are presented in this paper. A general lack of gaseous NH₃ was found in these cloud systems, which caused a lack of buffer capacity toward acid addition. Evidence supports the hypothesis that the higher acidity of the cloud systems during this final period of the campaign was due to input of HNO₃. Our measurements, however, could not determine whether the observed input was due to scavenging of gaseous HNO₃ from the air feeding into the cloud, or to heterogeneous HNO₃ formation via NO₂ oxidation by O₃ to NO₃ and N₂O₅. Sulfate in cloud droplets mainly originated from aerosol SO ₄ ^2– scavenging, since S(IV) to S(VI) liquid phase conversion was inhibited due to both lack of H₂O₂ and low pH of cloud droplets, which made O₃ and metal catalyzed S(IV) oxidation inefficient.     

华北地区气溶胶混合状态对暖云微物理特征的影响

在UWyo单组分气溶胶的绝热气块分档云模式基础上,发展了多种化学组分气溶胶的绝热气块分档云模式。利用2006年春季华北地区地面气溶胶分级采样的离子成分分析数据和同时段高空气溶胶、云微物理飞机观测资料,研究了气溶胶混合状态对暖云微物理特征的影响。模拟结果表明,华北地区气溶胶内部混合比外部混合有利于增加云凝结核数浓度、降低气块水汽最大饱和比、增加云滴数浓度。气溶胶的混合状态不同,形成的云滴谱的特征差异较大,主要体现在云滴谱的平均尺度和峰值的突出程度;云滴谱相对离散度在0.3附近变化,且随着云滴数浓度的增加,云滴谱相对离散度呈现减小的趋势。气溶胶混合状态能够影响暖云微物理特征,从而影响大气辐射和降水过程,在天气和气候变化的研究中应予以关注。     

A modeling study of the effects of aerosols on clouds and precipitation over East Asia

The National Center for Atmospheric Research Community Atmosphere Model (version 3.5) coupled with the Morrison?CGettelman two-moment cloud microphysics scheme is employed to simulate the aerosol effects on clouds and precipitation in two numerical experiments, one representing present-day conditions (year?2000) and the other the pre-industrial conditions (year?1750) over East Asia by considering both direct and indirect aerosol effects. To isolate the aerosol effects, we used the same set of boundary conditions and only altered the aerosol emissions in both experiments. The simulated results show that the cloud microphysical properties are markedly affected by the increase in aerosols, especially for the column cloud droplet number concentration (DNC), liquid water path (LWP), and the cloud droplet effective radius (DER). With increased aerosols, DNC and LWP have been increased by 137% and 28%, respectively, while DER is reduced by 20%. Precipitation rates in East Asia and East China are reduced by 5.8% and 13%, respectively, by both the aerosol??s second indirect effect and the radiative forcing that enhanced atmospheric stability associated with the aerosol direct and first indirect effects. The significant reduction in summer precipitation in East Asia is also consistent with the weakening of the East Asian summer monsoon, resulting from the decreasing thermodynamic contrast between the Asian landmass and the surrounding oceans induced by the aerosol??s radiative effects. The increase in aerosols reduces the surface net shortwave radiative flux over the East Asia landmass, which leads to the reduction of the land surface temperature. With minimal changes in the sea surface temperature, hence, the weakening of the East Asian summer monsoon further enhances the reduction of summer precipitation over East Asia.     

CAM3.0模式中黑碳及硫酸盐气溶胶浓度变化对东亚春季气候的影响研究

本文采用CAM3.0模式研究东亚地区各种气溶胶浓度增加后对于东亚春季各气候要素,尤其是对降水和春季风场的影响。在模式中通过分别对区域(20～50°N,100～150°E)内黑碳气溶胶浓度单独加倍、硫酸盐气溶胶浓度单独加倍、两种气溶胶浓度同时加倍的实验方法,探讨不同气溶胶浓度变化在东亚春季气候变化中的具体作用。结果表明:在春季,3种气溶胶浓度增加方式都使得东亚地区表现出降水中南部减少北部增加,低层大气西南风异常以及地面温度南部增加北部减少。通过对110～120°E的断面分析发现,硫酸盐与黑碳气溶胶在春季首先影响约800 hPa以上大气的温度并通过不同的动力机制影响东亚地区的风场,风场的改变进而导致了云量和降水在东亚北方地区增多而中南部地区减少,并最终使得地面温度表现出东亚中南部地区增温而北方地区相对降温的特征。     

Oligomerization of levoglucosan by Fenton chemistry in proxies of biomass burning aerosols

Reactions of levoglucosan with produced from Fenton chemistry were studied in solution serving as a proxy for biomass burning aerosols. Two modes of oligomerization (≤2000 u) were observed for reaction times between 1 and 7 days using matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF-MS) and laser desorption ionization time-of-flight mass spectrometry (LDI-TOF-MS). Single-mass unit continuum mass distributions with dominant −2 u patterns were measured and superimposed by a +176/+162 u oligomer series. This latter oligomer pattern was attributed to a Criegee rearrangement (+14 u) of levoglucosan, initiated by , forming a lactone (176 u). The acid-catalyzed reaction of any ROH from levoglucosan (+162 u) forms an ester through transesterification of the lactone functionality, whereupon propagation forms polyesters. Proposed products and chemical mechanisms are suggested as sources and precursors of humic-like substances (HULIS), which are known to possess a large saccharic component and are possibly formed from biomass burning aerosols (Andreae, Global Biomass Burning, MIT Press, Cambridge, Massachusetts, 3–21, 1991).     

黄山地区春夏季气溶胶离子组分及其对云微物理特征的影响

利用2009年5-8月在华东地区高山——黄山顶取得的气溶胶和云微物理参数观测资料以及同期气溶胶离子成分数据,结合多种化学组分气溶胶绝热气块分档云模式,研究了黄山地区多化学组分气溶胶对云凝结核和云微物理特征的影响.气团轨迹和气溶胶离子成分的分析结果表明,3种气团影响着黄山地区气溶胶的化学组分,即北方大陆气团气溶胶富含CaCO3,局地污染气团气溶胶以可水溶性无机盐((NH4)2SO4、NH4 NO3)为主,而变性混合海洋性气团气溶胶中NaCl较多.数值模拟结果显示,在气溶胶谱一定时,不同天气形势下黄山气溶胶的化学组分的差异会对云微物理特征产生不同的影响.同一上升速度下实际多组分气溶胶模拟的云滴数浓度大于纯硫酸铵,主要体现在云滴谱第1个峰值3.3 μm之前;气块上升速度低于0.7 m/s时,含有较多不可水溶物质的混合气溶胶对云滴数浓度的影响较大;上升速度大于0.7 m/s时,气块中可凝结水增多,海盐对云滴数浓度增加的效果更显著.多组分气溶胶模拟云滴谱较纯硫酸铵窄,其中,北方气团方案造成云滴谱变窄的程度高于混合气团方案;而模拟的云滴数目增多,造成云滴有效半径减小,云光学厚度和反照率增加,将会对暖云降水及辐射效应产生不同的影响.     

山地对流云并合形成积层混合云的过程分析

本文利用贵阳市气象台2005和2006年5-9月的地面、高空观测和雷达资料等,分析了41次山地对流云并合形成积层混合云的降水过程.研究发现如果分散的多单体对流云若距离较近,则很可能出现大范围地跨接、合并,则有可能形成范围宽广的片状或带状云系,即积层混合云系.云系形成以后在移动的过程中,会将前方不断新生的对流单体合并,从而云系前缘强度增强,云系不断维持.整个系统的生命期往往较分散云团更长,并有可能会形成间歇性或连续性降水.本文分析了山地对流云并合形成积层混合云的一些具体特征.     

Modelling of the nighttime nitrogen and sulfur chemistry in size resolved droplets of an orographic cloud

A chemistry module has been incorporated into a Lagrangian type model that computes the dynamics and microphysics of an orographical cloud formed in moist air flowing over the summit of Great Dun Fell (GDF) in England. The cloud droplets grow on a maritime aerosol which is assumed to be an external mixture of sea-salt particles and ammonium-sulfate particles. The dry particle radii are in the range 10 nm<r<1 µm. The gas-phase chemical reaction scheme considers reactions of nitrogen compounds that are important at night. The treatment of scavenging of gases into the aqueous phase in the model takes into account the different solubilities and accommodation coefficients. The chemistry in the aqueous phase focusses on the oxidation of S(IV) via different pathways.Sensitivity analyses have been performed to investigate deviations from gas-liquid equilibria according to Henry's law and also to study the influence of iron and of nitrogen compounds on the aqueous-phase oxidation of dissolved SO₂. When addressing these questions, special attention has been given to the dependence on the droplet size distribution and on the chemical composition of the cloud condensation nuclei on which the droplets have formed. It was found that the oxidation of S(IV) via a chain reaction of sulfur radicals can be important under conditions where H₂O₂ is low. However, major uncertainties remain with respect to the interaction of iron with the radical chain. It was shown that mixing of individual cloud droplets, which are not in equilibrium according to Henry's law, can result in a bulk sample in equilibrium with the ambient air. The dependence of the aqueous-phase concentrations on the size of the cloud droplets is discussed for iron, chloride and NO₃.     

Characterization of organic aerosols in Beijing using an aerodyne high-resolution aerosol mass spectrometer

Fine particle of organic aerosol(OA), mostly arising from pollution, are abundant in Beijing. To achieve a better understanding of the difference in OA in summer and autumn, a high-resolution time-of-flight aerosol mass spectrometer(HRTo F-AMS, Aerodyne Research Inc., USA) was deployed in urban Beijing in August and October 2012. The mean OA mass concentration in autumn was 30 ± 30 μg m-3, which was higher than in summer(13 ± 6.9 μg m-3). The elemental analysis found that OA was more aged in summer(oxygen-to-carbon(O/C) ratios were 0.41 and 0.32 for summer and autumn,respectively). Positive matrix factorization(PMF) analysis identified three and five components in summer and autumn, respectively. In summer, an oxygenated OA(OOA), a cooking-emission-related OA(COA), and a hydrocarbon-like OA(HOA)were indentified. Meanwhile, the OOA was separated into LV-OOA(low-volatility OOA) and SV-OOA(semi-volatile OOA);and in autumn, a nitrogen-containing OA(NOA) was also found. The SOA(secondary OA) was always the most important OA component, accounting for 55% of the OA in the two seasons. Back trajectory clustering analysis found that the origin of the air masses was more complex in summer. Southerly air masses in both seasons were associated with the highest OA loading, while northerly air masses were associated with the lowest OA loading. A preliminary study of OA components,especially the POA(primary OA), in different periods found that the HOA and COA all decreased during the National Day holiday period, and HOA decreased at weekends compared with weekdays.     

基于云雷达资料的那曲对流云粒子相态识别研究

本文利用第三次青藏高原大气科学试验的Ka波段云雷达资料,结合微波辐射计和探空资料,提出了以模糊逻辑算法为框架的相态识别方法,并利用那曲两个典型对流云个例对方法效果进行了分析。通过与前人方法的对比和对不同相态粒子回波强度谱的统计,进一步验证了本文方法的可靠性。结果表明:利用雷达功率谱资料反演下落末速度并代替径向速度作为相态识别的参量之一,可提升对流云内粒子相态分类结果的合理性。零度层亮带和抬升凝结高度参量的使用,能够进一步优化相态识别的初步结果。固态云粒子的下落末速度远低于相同反射率因子的降水粒子,多模态/多谱峰的谱形态特征能够帮助识别混合相态粒子。     

A methodology study of the validation of clouds in GCMs using ISCCP satellite observations

The cloudiness fields simulated by a general circulation model and a validation using the International Satellite Cloud Climatology Project (ISCCP) satellite observations are presented. An adapted methodology is developed, in which the issue of the sub-grid scale variability of the cloud fields, and how it may affect the comparison exercise, is considered carefully. In particular different assumptions about the vertical overlap of cloud layers are made, allowing us to reconstruct the cloud distribution inside a model grid column. Carrying out an analysis directly comparable to that of ISCCP then becomes possible. The relevance of this method is demonstrated by its application to the evaluation of the cloud schemes used in Laboratoire de Météoroligie Dynamique (LMD) general circulation model. We compare cloud properties, such as cloud-top height and cloud optical thickness, analysed by ISCCP and simulated by the LMD GCM. The results show that a direct comparison of simulated low cloudiness and that shown from satellites is not possible. They also reveal some model deficiencies concerning the cloud vertical distribution. Some of these features depend little on the cloud overlap assumption and may reveal inadequate parameterisation of the boundary layer mixing or the cloud water precipitation rate. High convective clouds also appear to be too thick.