气溶胶核化清除的化学效应 I：云滴化学非均匀性的研究

本文将水汽在云滴上凝结增长的物理过程与气溶胶、气体的化学过程相结合，对气溶胶核化清除的化学效应进行了研究。 计算结果表明:气溶胶的核化清除造成了云滴化学成分随云滴大小分布的非均匀性，这种非均匀性又对云滴内发生的气体吸收、液相氧化产生影响。 本文还比较了不同污染状况下，不同大小的云滴内气溶胶核化清除与液相氧化对云滴化学的相对贡献的差异。 因此，这种云滴化学的非均匀性(云微化学)的研究对于云化学的野外观测及数值模拟都是重要的。     

Absorption and desorption of dichloromethane vapor by water drops in air. An experimental test of scavenging theory

An experimental study of the scavenging of dichloromethane vapor by water drops falling at terminal velocity, has been carried out in the UCLA precipitation shaft, in order to test the predictions of theoretical washout models. Whereas good agreement between theory and experiment was found for drops of radius 0.332 mm, computed gas uptake rates for 1.253 and 2.21 mm radius drops were much slower than those measured, just as reported previously for the washout of both sulfur dioxide and acetaldehyde. An analysis shows that theory can be reconciled with all of the experimental data by replacing the compound specific aqueous phase Fickian molecular diffusion coefficient used in the theory, by an effective diffusivity, having a constant value, (3×10^-4 cm² s^-1), independent of the physical and chemical nature of the absorbed species, for all drops of equivalent radii greater than 0.9 mm.     

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.     

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.     

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     

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.     

Laboratory studies about the interaction of ammonia with ice crystals at temperatures between 0 and −20°C

In laboratory experiments the interactions of ammonia with ice crystals were studied within the temperature range between 0 and −20°C. In a first series of experiments dendritic ice crystals were grown from water vapor in presence of ammonia gas in various concentrations between 4 and 400 ppbv. In a second series of experiments pure ice crystals were exposed to a humidified ammonia–air mixture inside a horizontal flow tube. The influence of temperature, ammonia gas concentration (0.6, 1.5, and 10 ppmv), exposure time, and the presence of impurities such as sulfate on the ammonia uptake by the ice surface was investigated by determining the ammonium content in the melt water of the ice crystals by ion chromatography. During the growth of ice crystals significant amounts of ammonia (around 200 μg/l) were taken up even at small gas concentrations. In contrast, even at high gas concentrations the uptake of ammonia by non-growing ice crystals was lower by approximately one order of magnitude. The presence of sulfate on the ice surface affected an enhanced uptake of ammonia by a factor of 5–10. A model is presented which describes the uptake of ammonia by ice considering the chemical processes occurring in the ice surface layer and simultaneous diffusion of ammonia into bulk ice. Even the increased uptake of ammonia by growing ice is rather small compared to the uptake by water droplets; thus, the major process for scavenging of ammonia from the atmosphere via the ice phase might not be the direct uptake by ice crystals but the riming involving super-cooled droplets containing ammonia.     

The Uptake Coefficient of I2 on Various Aqueous Surfaces

Uptake coefficient of I₂ on aqueous surfaces was measured by using an impinging flow method. Dependence of the uptake coefficient on the gas-liquid contact time and pH was investigated. The uptake coefficient was (3.7± 2.0)×10^–4 at 120 ms, 293 K and pH = 5.6. In the alkaline region, the uptake coefficient was larger by one order of magnitude than that in the neutral and acidic region. The I₂ uptake on KI solutions and synthetic sea water solutions was also measured. According to the analysis by the reactive uptake model, the uptake of I₂ was shown to be mainly determined by liquid phase reactions and the accommodation coefficient of I₂ on aqueous surfaces was estimated to be 0.01.     

A comparison of scavenging and deposition processes in global models: results from the WCRP Cambridge Workshop of 1995

We report on results from a World Climate Research Program workshop on representations of scavenging and deposition processes in global transport models of the atmosphere. 15 models were evaluated by comparing simulations of radon, lead, sulfur dioxide, and sulfate against each other, and against observations of these constituents. This paper provides a survey on the simulation differences between models. It identifies circumstances where models are consistent with observations or with each other, and where they differ from observations or with each other. The comparison shows that most models are able to simulate seasonal species concentrations near the surface over continental sites to within a factor of 2 over many regions of the globe. Models tend to agree more closely over source (continental) regions than for remote (polar and oceanic) regions. Model simulations differ most strongly in the upper troposphere for species undergoing wet scavenging processes. There are not a sufficient number of observations to characterize the climatology (long‐term average) of species undergoing wet scavenging in the upper troposphere. This highlights the need for either a different strategy for model evaluation (e.g., comparisons on an event by event basis) or many more observations of a few carefully chosen constituents.     

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。     

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.     

积云对二氧化硫和硫酸盐气溶胶作用的研究

利用一个冰雹云模式与云化学模式耦合而成的二维积云化学模式,研究对流云的输送、微物理转化、云内化学过程、湿清除对SO2及硫酸盐气溶胶的作用。云化学模式的结果表明,由于SO2在向上输送的过程中可溶解于云水和雨水中,从而阻止了SO2向上部的转移,因此对气相SO2来说,云的输送是一个相当无效的过程,而液相清除起主要作用。硫酸盐气溶胶的收支分析表明,降水清除了1.67 mol的SO2-4,占气溶胶总量的64%,其中液态降水清除了0.72 mol,固态降水清除了0.95 mol,说明了冰相过程在硫沉降中的重要性。     

A two-moment parameterization of aerosol nucleation and impaction scavenging for a warm cloud microphysics: description and results from a two-dimensional simulation

A new two-moment warm bulk scheme has been developed including explicitly nucleation and impaction scavenging of aerosol particles as well as all other microphysical processes. The scheme is built upon a quasispectral representation of the aerosol particle, cloud droplet and raindrop distributions. It predicts mixing ratios and number concentrations for each category. Each process is treated explicitly and independently to establish an analytic expression for each contribution for the time-dependant microphysical equations. The scheme has been tested in the dynamical framework of a two-dimensional kinematic model, developed for the Hawaiian Rainband Project (HaRP, 1990). In this frame, the scheme has performed reasonably well compared to the observations as well as to other similar parameterization schemes, and to the spectral model DESCAM.Sensitivity tests demonstrate the great sensitivity of the scheme to the initial aerosol spectrum characteristics. Moreover, they have also shown its capability to calculate nucleation and impaction scavenging and to follow the taken up particle mass in the cloud and raindrop spectra until the deposition on the ground by the rain.Therefore, the parameterization offers a possibility of treating the evolution of the liquid phase of the cloud together with the aerosol particle scavenging. However, due to the severe limitations of a two-dimensional kinematic model, the scheme needs to be further validated in a three-dimensional dynamical model.     

On the diffusivity of trace gases under stratospheric conditions

Transport of trace gases within the gas phase to a cloud or a sulphate aerosol droplet proceeds by molecular diffusion at the gas-liquid interface. An accurate determination of the molecular diffusion coefficient has a direct bearing on estimates of trace gas uptake and scavenging. A literature search revealed that this parameter is often chosen rather arbitrarily and the choice of a particular value is constrained by the availability of experimental data which are usually available at one atmospheric pressure under laboratory conditions. Since the process of trace gas transport to droplets occur at heights much above the ground level, it is important to determine an accurate value of the diffusion coefficient at varying levels in the atmosphere. This was achieved theoretically by estimating diffusivities for some important trace gases under stratospheric conditions by a Lennard-Jones method. Molecular diffusivity of 22 trace gases (including ClONO₂, HNO₃, SO₂ and H₂O₂ which may lead to heterogeneous reactions on various surfaces) have been estimated which can be used by modellers for improved scavenging estimates.     

中国地区硫酸盐气溶胶的分布特征

建立了一个三维欧拉型排放/输送/转化/沉降模式,其主要特点是采用独立的气相化学子模式计算各种不同条件下SO2的转化速率,建立转化率的数据库,直接为欧拉模式调用,并对液相化学和湿清除过程进行了参数化处理。这样使模式既考虑了大气化学过程的非线性,又具有较高的计算效率,能够方便地计算年（季）尺度的硫酸盐气溶胶SO2-4的浓度分布。利用中尺度气象模式MM4和欧拉输送模式模拟了中国地区硫酸盐气溶胶的时空分布,其结果可以方便地应用到考虑硫酸盐气溶胶气候效应的气候模式中去。     

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.     

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。     

积云发展对酸化剂清除的数值模拟

本文利用云内成雨清除模式和云下雨水冲刷清除模式讨论了云内和云下致酸物质的清除、酸化过程。计算结果表明，雨不酸化主要是在云内形成、而云底之下雨水对清除酸化过程是不重要的。而对流引起的上升气流和下沉气流对污染层内致酸物质的浓度变化有较大影响。     

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.     

An evaluation of the ADOM cloud module

Abstract

The Acid Deposition and Oxidant Model (ADOM) is an Eulerian long‐range transport and deposition model. One of the most highly parametrized and least well established parts of the model is the scavenging module that describes cloud formation, pollutant scavenging, aqueous‐phase chemistry and wet deposition. As a means of gaining insight into the scavenging module, results from simulations with the module are compared with the results from simulations for equivalent conditions with a three‐dimensional dynamic cloud chemistry model.

Comparisons of results for a variety of initial conditions show that wet deposition of sulphate, nitrate and ammonium ions tend to be underpredicted by the scavenging module and that the pH of the rain is overpredicted. Although the differences are for the most part not large, they are sensitive to cloud top height. The amount of hydrogen peroxide deposited at the surface is significantly smaller in the ADOM module than in the cloud chemistry model. For the particular conditions that are considered, oxidation is limited by the hydrogen peroxide concentration for the cloud chemistry model, but by the sulphur dioxide concentration for the ADOM module.