Rapid change in nitrate and sulfate concentrations observed in early stage of precipitation and their deposition processes

The concentrations of H⁺, nitrate (NO₃ ^-), and sulfate (SO₄ ^2-) in rainwater and their temporal changes were analyzed on the basis of continuous observation from 1 July 1991 to 30 June 1992 at a suburb of Nagoya, Japan. The yearly average for pH was 4.4. In general, an increasing pH with increase in precipitation amount was observed for rain events. Relatively high pH rainwater was sometimes observed at the beginning of rainfall, even though high concentrations of NO₃ ^- and SO₄ ^2- were involved. The high pH values were considered to be caused by the neutralization process with particulate matter containing cations. The yearly averaged ratio of equivalent concentration of nitrate to sulfate (N/S) in rainwater was 0.58. In the early stage of rain, the N/S value was usually more than 1.0 due to the difference of scavenging process between NO₃ ^- and SO₄ ^2-. High values of N/S ranging from 5 to 10 were found under the atmospheric conditions of calm winds and low humidity, during which it is possible that atmospheric particles float for a long time in the air before a rain event. The adsorption of NO₃ ^- in the early stage of rainfall by particulate matter was suggested from the difference in scavenging processes of NO₃ ^- and SO₄ ^2-. A possible scavenging process, called limb cloud scavenging, is presented to explain the interaction of particles and nitrate ions at the early stage of rain. In limb cloud scavenging, the repeated migration of cloud particles or raindrops between the inside and outside of clouds increases the absorption of ions to a highly condensed level, thus increasing the N/S value of rainwater. The influence of global scale seasonal phenomena with large amounts of particulates, such as typhoons or Asian dust storms, was also studied.     

云南4次热带系统影响强对流风暴卫星云图和地闪特征

利用NCEP再分析气象资料及FY-2E卫星云图、地闪、地面自动站和气象灾情等资料对热带系统影响下的4类强对流风暴卫星云图特征和地闪演变规律进行分析。结果表明:西移北抬的赤道辐合带、副高、热带低压等热带系统外围偏东、西南和东北气流为强对流风暴发生发展提供有利环流背景及充足水汽和较高的对流有效位能,800 hPa中尺度辐合线及风随高度顺转和高层反气旋低层气旋的垂直流场结构为强对流风暴提供动力条件;在高能高湿环境条件下,由于辐合抬升作用,对流单体生成、不断长大、有规律排列、相互合并发展成不同大小和形状的单单体风暴、多单体风暴、飑线、MCC,结构密实和不均匀,伴随激烈地闪的同时产生冰雹大风和短时强降水等强对流天气;4种类型强对流风暴云顶亮温与总、负、正闪频数随时间演变规律基本一致,正、负地闪活跃程度能表征强对流风暴发展演变状况,与云顶亮温之间存在较好的相关关系,总(负)地闪频数演变趋势与云顶亮温演变趋势相反。     

Precipitation Structures of a Thermal Convective System Happened in the Central Western Subtropical Pacific Anticyclone

In this paper, characteristics of precipitating clouds in a thermal convective system (TCS) occurred in the southeastern mainland of China at 15:00 BT (Beijing time) on August 2, 2003 in the central western subtropical Pacific anticyclone (WSPA) is studied by using TRMM tropical rainfallmeasuring mission PR (precipitution radar) and IR Infrared radiation measurements. The precipitating cloud structures in both horizontal and vertical, relationship among storm top, cloud top, and surface rain rate are particularly analyzed. Results show that a strong ascending air at 500 hPa and a strong convergence of moisture flux at 850 hPa in the central WSPA supply necessary conditions both in dynamics and moisture for the happening of the TCS precipitation. The TRMM PR observation shows that the horizontal scale of the most TCS precipitating clouds is about 30-40 km, their averaged vertical scale is above 10 km, and the maximum reaches 17.5 km. The maximum rain rate near surface of those TCS clouds is beyond 50 mm h-1. The mean rain profile of the TCS clouds shows that its maximum rain rate at 5 km altitude is 1 km lower than the estimated freezing level of the environment. Compared with the mesoscale convective system (MCS) of "98.7.20", both systems have the same altitude of the maximum rain rate displayed from both mean rain profiles, but the TCS is much deeper than the MCS. From the altitude of the maximum rain rate to near surface, profiles show that rain rate reducing in the TCS is faster than that in the MCS, which implies a strong droplet evaporation process occurring in the TCS. Relationship among cloud top, storm top, and surface rain rate analysis indicates a large variation of cloud top when storm top is lower. On the contrary, the higher the storm top, the more consistent both cloud top and storm top. And, the larger the surface rain rate, the higher and more consistent for both cloud top and storm top. At the end, results expose that area fractions of non-precipitating clouds and clear sky are 86% and 2%, respectively. The area fraction of precipitating clouds is only about 1/8 that of non-precipitating clouds.     

大气冰核谱分布对对流风暴云人工催化影响的数值模拟研究

2002年9月在青海省河南县人工增雨综合试验基地开展了人工增雨外场综合观测试验.根据这次实验得到的大气冰核资料,以及文献给出的另外两组常用的冰核资料,利用中国科学院大气物理研究所研制和发展的三维对流云人工催化数值模式,讨论了3类不同大气冰核谱环境对模拟对流风暴云人工催化增雨效果的影响,模式中还考虑了国内人工影响天气部门常用的RYI-6300型和WR-1B型人工增雨防雹火箭播云弹道的差异.模拟结果表明,3类不同大气冰核谱环境对模拟对流风暴云的宏观和微观参量分布结构有很大影响,在这些对流云中进行火箭播云催化试验得到的播云效果也有很大差异.大气环境中高温冰核浓度低,而低温冰核浓度高时,对流风暴云人工催化将导致云中冰晶过量,不利于对流风暴云降水增加.在大气环境中高温冰核浓度较高,并且低温冰核浓度较低时,对流催化风暴云可获得最高的人工增雨效果.在青海试验区的大气冰核谱环境下,火箭催化对流风暴云增雨有一定效果.对不同地区进行人工增雨作业时,了解清楚当地大气冰核的基本背景状况对于正确地评估播云效果非常重要.文中还给出了导致这些结果差异的物理解释.     

Convective and Stratiform Cloud Rainfall Estimation from Geostationary Satellite Data

The Bayes Decision (BD) method was used to distinguish the corrective and stratiform components of cloud sys-tems from GMS-4 satellite data. A technique originally developed by Adler and Negri (1988, hereafter abbreviated AN) was improved for estimating the convective and stratiform cloud precipitation areas and rates of cloud systems from GMS satellite imagery. It has been applied to a tropical cyclonic cloud cluster observed over east coast area of China on September 23, 1992, which brought about flood disaster in that region. Overlaid 6-hour surface rainfall ob-servations show that the rainfall areas and amounts match with results from improved AN technique. The successful application of the Adler and Negri’s technique to convective and stratiform clouds provides encouragement for the use of this method over large region of mid-latitude China where radar data are not fully covered.     

Sources,transport, and sinks of SO<Subscript>2</Subscript> over the equatorial Pacific during the Pacific Atmospheric Sulfur Experiment

The Pacific Atmospheric Sulfur Experiment (PASE) is the first sulfur-budget field experiment to feature simultaneous flux measurements of DMS marine emissions and SO₂ deposition to the ocean surface. We make use of these data to constrain a 1-D chemical transport model to study the production and loss pathways for DMS and SO₂ over the equatorial Pacific. Model results suggest that OH is the main sink for DMS in the boundary layer (BL), and the average DMS-to-SO₂ conversion efficiency is ~73%. In an exploratory run involving the addition of 1 pptv of BrO as a second oxidant, a 14% increase in the DMS flux is needed beyond that based on OH oxidation alone. This BrO addition also reduces the DMS-to-SO₂ conversion efficiency from 73% to 60%. The possibility of non-DMS sources of marine sulfur influencing the estimated conversion efficiency was explored and found to be unconvincing. For BL conditions, SO₂ losses consist of 48% dry deposition, while transport loss to the BuL and aerosol scavenging each account for another 19%. The conversion of SO₂ to H₂SO₄ consumes the final 14%. In the BuL, cloud scavenging removes 85% of the SO₂, thus resulting in a decreasing vertical profile for SO₂. The average SO₂ dry deposition velocity from direct measurements (i.e., 0.36 cm sec⁻¹) is approximately 50% of what is calculated from the 1-D model and the global GEOS-Chem model. This suggests that the current generation of global models may be significantly overestimating SO₂ deposition rates over some tropical marine areas. Although the specific mechanism cannot be determined, speculation here is that the dry deposition anomalous results may point to the presence of a micro-surface chemical phenomenon involving partial saturation with either S(IV) and/or S(VI) DMS oxidation products. This could also appear as a pH drop in the ocean’s surface microfilm layer in this region. Finally, we propose that the enhanced SO₂ level observed in the lower free troposphere versus that in the upper BuL during PASE is most likely the result of transported DMS/SO₂-rich free-tropospheric air parcels from the east of the PASE sampling area, rather than an inadequate representation in the model of local convection.     

Sulfur dioxide in rain clouds: Gas-liquid scavenging efficiencies and wet deposition rates in the presence of formaldehyde

The interaction of formaldehyde with SO₂ dissolved in the aqueous phase of clouds leads to the formation of hydroxymethane sulfonate. The impact of this process upon the gas-liquid equilibrium distribution of SO₂ in rain clouds and the ensuing wet SO₂ precipitation rate is explored. Model vertical SO₂ distributions are derived from observational data for three atmospheric regions: continental polluted, continental remote, and marine. The wet deposition rate for SO₂ in the polluted atmosphere increases by about a factor of two in the presence of formaldehyde compared with its absence. The effect is much stronger in the remote atmosphere leading to a potentially significant enhancement of wet SO₂ deposition. In the marine atmosphere, wet deposition of SO₂ may contribute as much as 35% to the total removal rate for SO₂ by all processes including dry deposition and chemical conversion to sulfate.     

一次热带海洋对流云微物理过程的数值模拟

为了理解微物理过程以及次生对流云对热带对流云团发展演变过程的影响,利用二维云分辨模式对2006年1月20日靠近澳大利亚西北部的印度尼西亚暖池附近的一次对流云降水过程进行数值模拟,分析了对流云发展演变不同阶段各种微物理过程的特征,尤其对次生对流的形成以及并合过程进行了深入分析.结果表明:本个例所研究的热带对流云团具有发展...     

登陆过程中热带风暴"黄蜂"螺旋云带的分析

分析了热带风暴"黄蜂"在登陆过程中逐小时高分辨红外云图上的螺旋云带及其强对流云团的变化规律.从强对流云团发展为主螺旋云带的演变过程中,螺旋云带主要表现为其前端的对流逐渐加强,其余部分逐渐减弱,以及前端的强对流云团总体表现为旋入运动且维持时间较长,而其余部分的云团总体表现为远离中心等的特征.初步探讨了螺旋云带结构变化与风暴强度之间的关系和"黄蜂"在登陆后迅速减弱的可能原因.     

A process oriented characterization of tropical oceanic clouds for climate model evaluation, based on a statistical analysis of daytime A-train observations

This paper aims at characterizing how different key cloud properties (cloud fraction, cloud vertical distribution, cloud reflectance, a surrogate of the cloud optical depth) vary as a function of the others over the tropical oceans. The correlations between the different cloud properties are built from 2?years of collocated A-train observations (CALIPSO-GOCCP and MODIS) at a scale close to cloud processes; it results in a characterization of the physical processes in tropical clouds, that can be used to better understand cloud behaviors, and constitute a powerful tool to develop and evaluate cloud parameterizations in climate models. First, we examine a case study of shallow cumulus cloud observed simultaneously by the two sensors (CALIPSO, MODIS), and develop a methodology that allows to build global scale statistics by keeping the separation between clear and cloudy areas at the pixel level (250, 330?m). Then we build statistical instantaneous relationships between the cloud cover, the cloud vertical distribution and the cloud reflectance. The vertical cloud distribution indicates that the optically thin clouds (optical thickness <1.5) dominate the boundary layer over the trade wind regions. Optically thick clouds (optical thickness >3.4) are composed of high and mid-level clouds associated with deep convection along the ITCZ and SPCZ and over the warm pool, and by stratocumulus low level clouds located along the East coast of tropical oceans. The cloud properties are analyzed as a function of the large scale circulation regime. Optically thick high clouds are dominant in convective regions (CF?>?80?%), while low level clouds with low optical thickness (<3.5) are present in regimes of subsidence but in convective regimes as well, associated principally to low cloud fractions (CF?<?50?%). A focus on low-level clouds allows us to quantify how the cloud optical depth increases with cloud top altitude and with cloud fraction.     

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.     

Pacific Atmospheric Sulfur Experiment (PASE): dynamics and chemistry of the south Pacific tropical trade wind regime

The Pacific Atmospheric Sulfur Experiment (PASE) was a comprehensive airborne study of the chemistry and dynamics of the tropical trade wind regime (TWR) east of the island of Kiritibati (Christmas Island, 157º, 20?? W, 2º 52?? N). Christmas Island is located due south of Hawaii. Geographically it is in the northern hemisphere yet it is 6?C12º south of the intertropical convergence zone (ITCZ) which places it in the southern hemisphere meteorologically. Christmas Island trade winds in August and September are from east south east at 3?C15 ms^?1. Clouds, if present, are fair weather cumulus located in the middle layer of the TWR which is frequently labeled the buffer layer (BuL). PASE provided clear support for the idea that small particles (80 nm) were subsiding into the tropical trade wind regime (TWR) where sulfur chemistry transformed them to larger particles. Sulfur chemistry promoted the growth of some of these particles until they were large enough to activate to cloud drops. This process, promoted by sulfur chemistry, can produce a cooling effect due to the increase in cloud droplet density and changes in cloud droplet size. These increases in particle size observed in PASE promote additional cooling due to direct scattering from the aerosol. These potential impacts on the radiation balance in the TWR are enhanced by the high solar irradiance and ocean albedo of the TWR. Finally because of the large area involved there is a large factional impact on earth??s radiation budget. The TWR region near Christmas Island appears to be similar to the TWR that persists in August and September, from southwest of the Galapagos to at least Christmas Island. Transport in the TWR between the Galapagos and Christmas involves very little precipitation which could have removed the aerosol thus explaining at least in part the high concentrations of CCN (??300 at 0.5% supersaturation) observed in PASE. As expected the chemistry of sulfur in the trade winds was found to be initiated by the emission of DMS into the convective boundary layer (BL, the lowest of three layers). However, the efficiency with which this DMS is converted to SO₂ has been brought into further question by this study. This unusual result has come about as result of our using two totally different approaches for addressing this long standing question. In the first approach, based on accepted kinetic rate constants and detailed steps for the oxidation of DMS reflecting detailed laboratory studies, a DMS to SO₂ conversion efficiency of 60?C73% was determined. This range of values lies well within the uncertainties of previous studies. However, using a completely different approach, involving a budget analysis, a conversion value of 100% was estimated. The latter value, to be consistent with all other sulfur studies, requires the existence of a completely independent sulfur source which would emit into the atmosphere at a source strength approximately half that measured for DMS under tropical Pacific conditions. At this time, however, there is no credible scientific observation that identifies what this source might be. Thus, the current study has opened for future scientific investigation the major question: is there yet another major tropical marine source of sulfur? Of equal importance, then, is the related question, is our global sulfur budget significantly in error due to the existence of an unknown marine source of sulfur? Pivotal to both questions may be gaining greater insight about the intermediate DMS oxidation species, DMSO, for which rather unusual measurements have been reported in previous marine sulfur studies. The 3 pptv bromine deficit observed in PASE must be lost over the lifetime of the aerosol which is a few days. This observation suggests that the primary BrO production rate is very small. However, considering the uncertainties in these observations and the possible importance of secondary production of bromine radicals through aerosol surface reactions, to completely rule out the importance of bromine chemistry under tropical conditions at this time cannot be justified. This point has been brought into focus from prior work that even at levels of 1 pptv, the effect of BrO oxidation on DMS can still be quite significant. Thus, as in the case of DMS conversion to SO₂, future studies will be needed. In the latter case there will need to be a specific focus on halogen chemistry. Such studies clearly must involve specific measurements of radical species such as BrO.     

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 global three-dimensional model of the tropospheric sulfur cycle

The tropospheric part of the atmospheric sulfur cycle has been simulated in a global three-dimensional model. The model treats the emission, transport, chemistry, and removal processes for three sulfur components; DMS (dimethyl sulfide), SO₂ and SO₄ ^2– (sulfate). These processes are resolved using an Eulerian transport model, the MOGUNTIA model, with a horizontal resolution of 10° longitude by 10° latitude and with 10 layers in the vertical between the surface and 100 hPa. Advection takes place by climatological monthly mean winds. Transport processes occurring on smaller space and time scales are parameterized as eddy diffusion except for transport in deep convective clouds which is treated separately. The simulations are broadly consistent with observations of concentrations in air and precipitation in and over polluted regions in Europe and North America. Oxidation of DMS by OH radicals together with a global emission of 16 Tg DMS-S yr^–1 from the oceans result in DMS concentrations consistent with observations in the marine boundary layer. The average turn-over times were estimated to be 3, 1.2–1.8, and 3.2–6.1 days for DMS, SO₂, and SO₄ ^2– respectively.     

A comprehensive meteorological modeling system—RAMS

Summary This paper presents a range of applications of the Regional Atmospheric Modeling System (RAMS), a comprehensive mesoscale meterological modeling system. Applications discussed in this paper include large eddy simulations (LES) and simulations of thunderstorms, cumulus fields, mesoscale convective systems, mid-latitude cirrus clouds, winter storms, mechanically- and thermally-forced mesoscale systems, and mesoscale atmospheric disperision. A summary of current RAMS options is also presented. Improvements to RAMS currently underway include refinements to the cloud radiation, cloud microphysics, cumulus, and surface soil/vegetative parameterization schemes, the parallelization of the code, development of a more versatile visualization capability, and research into meso--scale cumulus parameterization.With 18 Figures     

Model Simulations on the Variability of Particulate MSA to Non-Sea-Salt Sulfate Ratio in the Marine Environment

A box model was constructed to investigate connections between the particulate MSA to non-sea-salt sulfate ratio, R, and DMS chemistry in a clean marine boundary layer. The simulations demonstrated that R varies widely with particle size, which must be taken into account when interpreting field measurements or comparing them with each other. In addition to DMS gas-phase chemistry, R in the submicron size range was shown to be sensitive to the factors dictating sulfate production via cloud processing, to the removal of SO₂ from the boundary layer by dry deposition and sea-salt oxidation, to the entrainment of SO₂ from the free troposphere, to the relative concentration of sub- and supermicron particles, and to meteorology. Three potential explanations for the increase of R toward high-latitudes during the summer were found: larger MSA yields from DMS oxidation at high latitudes, larger DMSO yields from DMS oxidation followed by the conversion of DMSO to MSA at high latitudes, or lower ambient H₂O₂ concentrations at high latitudes leading to less efficient sulfate production in clouds. Possible reasons for the large seasonal amplitude of R at mid and high latitudes include seasonal changes in the partitioning of DMS oxidation to the OH and NO₃ initiated pathways, seasonal changes in the concentration of species participating the DMS-OH reaction pathway, or the existence of a SO₂ source other than DMS oxidation in the marine boundary layer. Even small anthropogenic perturbations were shown to have a potential to alter the MSA to non-sea-salt sulfate ratio.     

Model studies of the impact of chemical inhomogeneity on SO2 oxidation in warm stratiform clouds

A one-dimensional, time-dependent model of the physics and chemistry of a warm stratiform cloud is used to study the possible impact of chemical inhomogeneity among cloud and raindrops on the oxidation of SO₂ in clouds. The effects of chemical inhomogeneity are examined using two contrasting models: In Model 1 a bulk-solution parameterization is adopted which effectively treats all cloud and raindrops as if they are chemically homogeneous; in Model 2 we allow the cloud and raindrops to have a dichotomous distribution. The dichotomous distribution in Model 2 is simulated by assuming that the two groups of cloud droplets nucleate from two chemically distinct populations of condensation nuclei; one being acidic and the other being alkaline. While the two models yield essentially identical results when the ambient levels of H₂O₂ are greater than the ambient levels of SO₂, the rate of conversion of SO₂ to sulfuric acid and the amount of sulfate removed in the precipitation can be significantly enhanced in Model 2 over that of Model 1 under conditions of oxidant limitation (i.e., H₂O₂ < SO₂). This enhancement is critically dependent upon the fraction of alkaline nuclei assumed to be present in Model 2 and arises from the rapid increase in the aqueous-phase reaction between O₃+S_IV at high pH. Our results suggest that cloud models which adopt a bulk-solution parameterization for cloud droplet chemistry, may underestimate the amount of in-cloud SO₂ oxidation under oxidant-limited conditions.     

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.     

Pollutant scavenging in a mesoscale meteorological model with quasi-spectral microphysics

Pollutant scavenging parameterizations have been combined with meteorological predictions in a three-dimensional mesoscale numerical model (1). This meteorological model with detailed quasi-spectral microphysics is well-suited to include gas and aerosol removal by cloud droplets and raindrops. Two-dimensional sensitivity tests have been performed for both meteorological and chemical scenarios. Both maritime and continental clouds over an idealized topography have been considered to determine their relative efficiencies for wet sulfur deposition. A second example deals with night-time nitric acid production which has been simulated in a case of moist advection. A threshold behaviour for NO₃ disappearance at relative humidities above 60 % was observed in agreement with experiments. The results obtained through such idealized tests emphasize the need for simultaneous treatment of dynamical, microphysical and physicochemical processes.     

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.