Modelling multiphase chemistry in deliquescent aerosols and clouds using CAPRAM3.0i

Modelling studies were performed with the multiphase mechanism RACM-MIM2ext/CAPRAM 3.0i to investigate the tropospheric multiphase chemistry in deliquesced particles and non-precipitating clouds using the SPACCIM model framework. Simulations using a non-permanent cloud scenario were carried out for two different environmental conditions focusing on the multiphase chemistry of oxidants and other linked chemical subsystems. Model results were analysed by time-resolved reaction flux analyses allowing advanced interpretations. The model shows significant effects of multiphase chemical interactions on the tropospheric budget of gas-phase oxidants and organic compounds. In-cloud gas-phase OH radical concentration reductions of about 90 % and 75 % were modelled for urban and remote conditions, respectively. The reduced in-cloud gas-phase oxidation budget increases the tropospheric residence time of organic trace gases by up to about 30 %. Aqueous-phase oxidations of methylglyoxal and 1,4-butenedial were identified as important OH radical sinks under polluted conditions. The model revealed that the organic C₃ and C₄ chemistry contributes with about 38 %/48 % and 8 %/9 % considerably to the urban and remote cloud / aqueous particle OH sinks. Furthermore, the simulations clearly implicate the potential role of deliquescent particles to operate as a reactive chemical medium due to an efficient TMI/HO_x,y chemical processing including e.g. an effective in-situ formation of OH radicals. Considerable chemical differences between deliquescent particles and cloud droplets, e.g. a circa 2 times more efficient daytime iron processing in the urban deliquescent particles, were identified. The in-cloud oxidation of methylglyoxal and its oxidation products is identified as efficient sink for NO₃ radicals in the aqueous phase.     

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.     

NUMERICAL MODELING OF CUMULUS CLOUD CHEMISTRY—PART Ⅰ.MODEL DEVELOPMENT*

A one-dimensional cumulus cloud chemistry model(ICCCM) is developed to simulate cloud physical processes and chemical processes during the evolution of a convective cloud.The cloud physical submodel includes a detailed microphysical parameterized scheme of 20 processes.The chemistry submodel is composed of three parts:gas phase chemistry,aqueous phase chemistry and scavenging of soluble gases.The gas phase reaction mechanism contains 85 reactions among 45 species including 13 organics.The aqueous phase reaction mechanism contains 54 reactions among 40 species and 12 ion equilibria.Mass of 19 gases is transported between the gas phase and the aqueous phase.With this model,studies may be made to analyze the interactions among processes during lifetime of a cumulus cloud.     

NUMERICAL MODELING OF CUMULUS CLOUD CHEMISTRY—PART Ⅰ.MODEL DEVELOPMENT

A one-dimensional cumulus cloud chemistry model(1CCCM)is developed to simulate cloudphysical processes and chemical processes during the evolution of a convective cloud.The cloudphysical submodel includes a detailed microphysical parameterized scheme of 20 processes.Thechemistry submodel is composed of three parts:gas phase chemistry,aqueous phase chemistry andscavenging of soluble gases.The gas phase reaction mechanism contains 85 reactions among 45species including 13 organics.The aqueous phase reaction mechanism contains 54 reactions among40 species and 12 ion equilibria.Mass of 19 gases is transported between the gas phase and theaqueous phase.With this model,studies may be made to analyze the interactions among processesduring lifetime of a cumulus cloud.     

The Great Dun Fell Experiment 1995: an overview

During March and April of 1995 a major international field project was conducted at the UMIST field station site on Great Dun Fell in Cumbria, Northern England. The hill cap cloud which frequently envelopes this site was used as a natural flow through reactor to examine the sensitivity of the cloud microphysics to the aerosol entering the cloud and also to investigate the effects of the cloud in changing the aerosol size distribution, chemical composition and associated optical properties. To investigate these processes, detailed measurements of the cloud water chemistry (including the chemistry of sulphur compounds, organic and inorganic oxidised nitrogen and ammonia), cloud microphysics and properties of the aerosol and trace gas concentrations upwind and downwind of the cap cloud were undertaken. It was found that the cloud droplet number was generally strongly correlated to aerosol number concentration, with up to 2000 activated droplets cm⁻³ being observed in the most polluted conditions. In such conditions it was inferred that hygroscopic organic compounds were important in the activation process. Often, the size distribution of the aerosol was substantially modified by the cloud processing, largely due to the aqueous phase oxidation of S(IV) to sulphate by hydrogen peroxide, but also through the uptake and fixing of gas phase nitric acid as nitrate, increasing the calculated optical scattering of the aerosol substantially (by up to 24%). New particle formation was also observed in the ultrafine aerosol mode (at about 5 nm) downwind of the cap cloud, particularly in conditions of low total aerosol surface area and in the presence of ammonia and HCl gases. This was seen to occur at night as well as during the day via a mechanism which is not yet understood. The implications of these results for parameterising aerosol growth in Global Climate Models are explored.     

Observed and modelled “chemical weather” during ESCOMPTE

The new MOdèle de Chimie Atmosphérique à Grande Echelle (MOCAGE) three-dimensional multiscale chemistry and transport model (CTM) has been applied to study heavy pollution episodes observed during the ESCOMPTE experiment. The model considers the troposphere and lower stratosphere, and allows the possibility of zooming from the planetary scale down to the regional scale over limited area subdomains. Like this, it generates its own time-dependent chemical boundary conditions in the vertical and in the horizontal. This paper focuses on the evaluation and quantification of uncertainties related to chemical and transport modelling during two intensive observing periods, IOP2 and IOP4 (June 20–26 and July 10–14, 2001, respectively). Simulations are compared to the database of four-dimensional observations, which includes ground-based sites and aircraft measurements, radiosoundings, and quasi-continuous measurements of ozone by LIDARs. Thereby, the observed and modelled day-to-day variabilities in air composition both at the surface and in the vertical have been assessed. Then, three sensitivity studies are conducted concerning boundary conditions, accuracy of the emission dataset, and representation of chemistry. Firstly, to go further in the analysis of chemical boundary conditions, results from the standard grid nesting set-up and altered configurations, relying on climatologies, are compared. Along with other recent studies, this work advocates the systematic coupling of limited-area models with global CTMs, even for regional air quality studies or forecasts. Next, we evaluate the benefits of using the detailed high-resolution emissions inventory of ESCOMPTE: improvements are noticeable both on ozone reactivity and on the concentrations of various species of the ozone photochemical cycle especially primary ones. Finally, we provide some insights on the comparison of two simulations differing only by the parameterisation of chemistry and using two state-of-the-art chemical schemes for regional photochemical modelling. Regional air quality modelling is found to be highly sensitive to the emission inventory dataset and also to the vertical and horizontal boundary conditions and detailed representation of chemistry. Interestingly enough, they infer the same range of errors compared to total model errors.     

Aqueous Phase Reaction of HNO4: The Impact on Tropospheric Chemistry

We use a global atmospheric chemistry transport model to study the possible influence of aqueous phase reactions of peroxynitric acid (HNO₄) on the concentrations and budgets of NO_x, SO_x, O₃ and H₂O₂. Laboratory studies have shown that the aqueous reaction of HNO_4aq withHSO^– _3aq, and the uni-molecular decomposition of the NO₄ ^– anion to form NO₂ ^– (nitrite) occur on a time scale of about a second. Despite a substantial contribution of the reaction of HSO^– _3aq with HNO_4aq to the overall in-cloud conversion of SO₂ to SO₄ ^2–, a simultaneous decrease of other oxidants (most notably H₂O₂) more than compensated the increase in SO₄ ^2– production. The strongest influence of heterogeneous HNO₄ chemistry was found in the boundary layer, where calculated monthly average ozone concentrations were reduced between 2% to 10% andchanges of H₂O₂ between –20% to +10%compared to a simulation which ignores this reaction. Furthermore, SO₂ was increased by 10% to 20% and SO₄ ^2–depleted by up to 10%. Since the resolution of our global model does not enable a detailed comparison with measurements in polluted regions, it is not possible to verify whether considering heterogeneous HNO₄ reactions results in a substantial improvement of atmospheric chemistry transport models. However, the conversion of HNO₄ in the aqueous phase seems to be efficient enough to warrant further laboratory investigations and more detailed model studies on this topic.     

Analysis of regional budgets of sulfur species modeled for the COSAM exercise

The COSAM intercomparison exercise (comparison of large‐scale sulfur models) was organized to compare and evaluate the performance of global sulfur cycle models. Eleven models participated, and from these models the simulated surface concentrations, vertical profiles and budget terms were submitted. This study focuses on simulated budget terms for the sources and sinks of SO₂ and sulfate in three polluted regions in the Northern Hemisphere, i.e., eastern North America, Europe, and Southeast Asia. Qualitatively, features of the sulfur cycle are modeled quite consistently between models, such as the relative importance of dry deposition as a removal mechanism for SO₂, the importance of aqueous phase oxidation over gas phase oxidation for SO₂, and the importance of wet over dry deposition for removal of sulfate aerosol. Quantitatively, however, models may show large differences, especially for cloud‐related processes, i.e., aqueous phase oxidation of SO₂ and sulfate wet deposition. In some cases a specific behavior can be related to the treatment of oxidants for aqueous phase SO₂ oxidation, or the vertical resolution applied in models. Generally, however, the differences between models appear to be related to simulated cloud (micro‐)physics and distributions, whereas differences in vertical transport efficiencies related to convection play an additional rôle. The estimated sulfur column burdens, lifetimes and export budgets vary between models by about a factor of 2 or 3. It can be expected that uncertainties in related effects which are derived from global sulfur model calculations, such as direct and indirect climate forcing estimates by sulfate aerosol, are at least of similar magnitude.     

区域酸性沉降的数值研究 I. 模式

建立了一个三维时变的欧拉型区域酸性污染物沉降模式，模式包括源排放、平流输送、湍流扩散、干沉积、气相化学、液相化学及湿清除等六大部分。考虑到计算条件的承受能力和应用性的要求，在把握酸沉降形成的关键过程的前提下，合理地简化设计模式。相对于国内已有的工作，本模式在干沉积、气相化学、液相化学和湿清除等方面均有所改进。     

Iodine Chemistry and its Role in Halogen Activation and Ozone Loss in the Marine Boundary Layer: A Model Study

A detailed set of reactions treating the gas and aqueous phase chemistry of the most important iodine species in the marine boundary layer (MBL) has been added to a box model which describes Br and Cl chemistry in the MBL. While Br and Cl originate from seasalt, the I compounds are largely derived photochemically from several biogenic alkyl iodides, in particular CH2I2, CH2ClI, C2H5I, C3H7I, or CH3I which are released from the sea. Their photodissociation produces some inorganic iodine gases which can rapidly react in the gas and aqueous phase with other halogen compounds. Scavenging of the iodine species HI, HOI, INO2, and IONO2 by aerosol particles is not a permanent sink as assumed in previous modeling studies. Aqueous-phase chemical reactions can produce the compounds IBr, ICl, and I2, which will be released back into the gas phase due to their low solubility. Our study, although highly theoretical, suggests that almost all particulate iodine is in the chemical form of IO-3. Other aqueous-phase species are only temporary reservoirs and can be re-activated to yield gas phase iodine. Assuming release rates of the organic iodine compounds which yield atmospheric concentrations similar to some measurements, we calculate significant concentrations of reactive halogen gases. The addition of iodine chemistry to our reaction scheme has the effect of accelerating photochemical Br and Cl release from the seasalt. This causes an enhancement in ozone destruction rates in the MBL over that arising from the well established reactions O(1D) + H2O 2OH, HO2 + O3 OH + 2O2, and OH + O3 HO2 + O2. The given reaction scheme accounts for the formation of particulate iodine which is preferably accumulated in the smaller sulfate aerosol particles.     

欧拉型区域硫沉降模式研究

建立了一个三维硫沉降欧拉模式，模式中比较全面地考虑了硫沉降过程中的物理、化学机制。包括平流、扩散、干湿沉降和积云的垂直输送作用等物理过程，气相化学、液相化学和气溶胶表面的非均相化学等化学过程。其中非均相化学和积云的垂直输送参数化在国内外同类模式中尚不多见。模式结果与实测及其他模式结果的对比表明，该模式能够较好地模拟出SO2的水平和垂直分布及SO2-4在降水中的浓度。     

Multi-Phase Chemistry of C<Subscript>2</Subscript> and C<Subscript>3</Subscript> Organic Compounds in the Marine Atmosphere

A box model is used to explore the detailed chemistry of C₂ and C₃ organic compounds in the marine troposphere by tracing the individual reaction paths resulting from the oxidation of ethane, ethene, acetylene, propane, propene and acetic acid. The mechanisms include chemical reactions in the gas phase and in the aqueous phase of clouds and aerosol particles at cloud level under conditions resembling those in the northern hemisphere. Organic hydroperoxides are found to be important intermediate products, with subsequent reactions leading partly to the formation of mixed hydroxy or carbonyl hydroperoxides that are readily absorbed into cloud water, where they contribute significantly to the formation of multifunctional organic compounds and organic acids. Organic hydroperoxides add little to the oxidation of sulfur dioxide dissolved in the aqueous phase, which is dominated by H₂O₂. Next to acetaldehyde and acetone, glycol aldehyde, glyoxal, methyl glyoxal and hydroxy propanone are prominent oxidation products in the gas and the aqueous phase. Acetaldehyde is not efficiently converted to acetic acid in clouds; the major local sources of acetic acid are gas-phase reactions. Other acids produced include hydroperoxy acetic, glycolic, glyoxylic, oxalic, pyruvic, and lactic acid. The mechanism of Schuchmann et al. (1985), which derives glycolic and glyoxylic acid from the oxidation of acetate, is found unimportant in the marine atmosphere. The principal precursors of glyoxylic acid are glyoxal and glycolic acid. The former derives mainly from acetylene and ethene, the latter from glycolaldehyde, also an oxidation product of ethene. The oxidation of glyoxylic acid leads to oxalic acid, which accumulates and is predicted to reach steady state concentrations in the range 30–90 ng m⁻³. This is greater, yet of the same magnitude, than the concentrations observed over the remote Pacific Ocean.     

Tropospheric ozone chemistry. The impact of cloud chemistry

The effect of clouds and cloud chemistry on tropospheric ozone chemistry is tested out in a two-dimensional channel model covering a latitudinal band from 30 to 60° N. Three different methods describing how clouds affect gaseous species are applied, and the results are compared. The three methods are:

?A first order parameterization scheme for the removal of sulphur and other soluble gases by liquid droplets.

?A parameterization scheme for SO₂, O₃, and H₂O₂ removal is constructed. The scheme is based on the solubility of gases in liquid droplets, cycling times of air masses between clouds and cloud free areas and on the chemical interaction of SO₂ with H₂O₂ and O₃ in the liquid phase.

?Gas-aqueous-phase interactions and aqueous-phase chemical reactions are included in the reaction scheme for a number of components in areas where clouds are present.

In all three methods, a full gas-phase chemistry scheme is used. Particular emphasis is given to the study of how the ozone and hydrogen peroxide levels are affected. Significant changes in the distributions are found when aqueous-phase chemical reactions are included. The result is loss of ozone in the aqueous phase, with pronounced reductions in ozone levels in the middle and lower troposphere. Ozone levels are reduced by 10 to 30% with the largest reductions in the remote middle troposphere, bringing the values in better agreement with observations. Changes in H₂O₂ are harder to predict. Although, in one case study, hydrogen peroxide is produced within the aqueous phase, concentrations are mostly comparable or even lower than in the other cases. Hydrogen peroxide levels are, however, shown to be very pH sensitive. pH values around 5 seem to favour high H₂O₂ levels. High H₂O₂ concentrations may be found particularly in the upper part of the clouds under favourable conditions.     

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.     

A Coupled Hydrophobic-Hydrophilic Model for Predicting Secondary Organic Aerosol Formation

The formation of secondary organic aerosol (SOA) results from the absorption of gas-phase organic oxidation products by airborne aerosol. Historically, modeling the formation of SOA has relied on relatively crude estimates of the capability of given parent hydrocarbons to form SOA. In more recent work, surrogate organic oxidation products have been separated into two groups, hydrophobic and hydrophilic, depending on whether the product is more likely to dissolve into an organic or an aqueous phase, respectively. The surrogates are then allowed to partition only via the dominant mechanism, governed by molecular properties of the surrogate molecules. The distinction between hydrophobic and hydrophilic is based on structural and physical characteristics of the compound. In general, secondary oxidation products, because of low vapor pressures and high polarities, express affinity for both the organic and aqueous aerosol phases. A fully coupled hydrophobic-hydrophilic organic gas-particle partitioning model is presented here. The model concurrently achieves mass conservation, equilibrium between the gas phase and the organic aerosol phase, equilibrium between the gas phase and the aqueous aerosol phase, and equilibrium between molecular and ionic forms of the partitioning species in the aqueous phase. Simulations have been performed using both a zero-dimensional model and the California Institute of Technology three-dimensional atmospheric chemical transport model. Simultaneous partitioning of species by both mechanisms typically leads to a shift in the distribution of products to the organic aerosol phase and an increase in the total amount of SOA predicted as compared to previous work in which partitioning is assumed to occur independently to organic and aqueous phases.     

Vegetation Feedback at the Mid-Pliocene

A global atmospheric general circulation model and an asynchronously coupled global atmosphere-biome model are used to simulate vegetation feedback at the mid-Pliocene approximately 3.3 to 3.0 million years ago.For that period,the simulated vegetation differed from present conditions at 62%of the global ice-free land surface.Vegetation feedback had little overall impact on the global climate of the mid-Pliocene.At the regional scale,however,the interactive vegetation led to statistically significant increases in annual temperature over Greenland,the high latitudes of North America,the mid-high latitudes of eastern Eurasia,and western Tibet,and reductions in most of the land areas at low latitudes,owing to vegetation-induced changes in surface albedo.     

云对云中大气臭氧影响因子的分析

应用一个较详细的气相光化学和液相化学耦合的箱体模式, 研究了云层对云中大气臭氧的影响过程。这一过程可分解为三个因子来考虑： 因子Ａ （云的辐射效应）, 由于云的存在改变太阳光辐射通量, 使得对流层光化学反应减弱或增强, 从而降低或增加臭氧浓度; 因子Ｂ（云的吸收效应）, 云层中液态水对大气臭氧及其前体物 （ＮＯｘ、ＮＭＨＣ、自由基等） 的直接吸收作用; 因子Ｃ（云的液相化学效应）, 吸收进入云中的物质发生液相化学反应从而改变大气臭氧浓度。数值研究结果表明： 上述三因子对云中臭氧浓度影响的程度差别很大, 并且与云层的物理结构有密切关系。讨论了云的吸收及液相化学效应影响臭氧浓度的主要原因     

Investigation of splitting gas and aqueous operators in atmospheric multiphase box models

Operator splitting techniques are widely used in atmospheric modeling in order to reduce the cost of time integration and allow more flexibility by treating each operator separately. However, this is not error free and the magnitude of the error depends on whether the splitted operators commute or not and the magnitude of the splitting time step. In multiphase models, the gas and the aqueous phase chemistries are related through the gas-droplet mass transfer processes. In the present paper, we show that splitting the gas chemistry operator from the aqueous chemistry and mass transfer operator is not appropriate and leads to errors beyond the tolerated thresholds. Analytical expressions for the splitting errors are derived and numerical experiments are conducted. The LAMP chemical mechanism is employed. Time integration is performed with LSODE.     

Speciation and role of iron in cloud droplets at the puy de Dôme station

Iron is the most abundant transition metal in the atmosphere and can play a significant role in cloudwater chemistry where its reactivity is closely related to the partitioning between Fe(II) and Fe(III). The objective of this work is to determine the total iron content and the iron speciation in a free tropospheric site, and to understand which factors influence these parameters. We collected 147 samples of cloudwater during 34 cloud events over a period of four years at the puy de Dôme summit. Besides iron we measured other chemical compounds, solar radiation, physico-chemical and meteorological parameters potentially connected with iron reactivity. The total iron concentrations ranged from 0.1 to 9.1 μM with the major frequency occurring at low levels. The pH and presence of organic complexants seem to be the most significant factors connected with total dissolved iron; while the iron oxidation state seems to be an independent factor. Light intensity, presence of complexants or oxidants (H₂O₂) do not influence the Fe(II)/Fe(Total) ratio, that was quite constant at about 0.75. This could be due to the potential redox that forces the Fe(II)-Fe(III) couple to the reduced form or, more probably to the complexation by Natural Organic Matter, that can stabilize iron in its reduced form and prevent further oxidation. Our field measurements did not show the diurnal cycle observed in surface water and predicted by models of atmospheric chemistry. This result prompts a more careful review of the role of iron and, by analogy, all the transition metals in atmospheric liquid phase, often over-estimated in the literature.