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.     

The interpretation of baseline atmospheric turbidity measurements at Cape Grim,Tasmania

Five years of turbidity data at Cape Grim have been analysed. The turbidity at 500 nm in clean maritime airmasses from the South to the West shows a seasonal variation, with a minimum in winter. There is also a variation in turbidity with wind speed. The winter minimum can be explained partially by a minimum in wind strength in that season. On the assumption, based on observations at Cape Grim and at other locations, that the boundary layer turbidity is caused by seasalt haze, an attempt is made to interpret the observed turbidity values and their seasonal changes. Optical extinction coefficients at the surface deduced from the measured values of optical depth are compared with extinction coefficients calculated from Mie theory using particle size distributions measured at Cape Grim. Reasonable agreement is obtained when the growth of salt particles in the high maritime humidity is considered, using both theoretical models and previous experimental results together with the rapid increase in salt concentration with wind speed.     

Ozone in the Marine Boundary Layer at Cape Grim: Model Simulation

A photochemical box model has been used to simulate the mixing ratio ofozone under conditions reflecting those encountered in the marine boundarylayer at Cape Grim, Tasmania, where a decade-long record of ozone mixingratio is available. The model is based on the proposition that ozone loss byphotolysis, atmospheric reaction with hydroperoxy and hydroxyl radicals, andsurface deposition is balanced by ozone gain via entrainment from the lowerfree troposphere with a small additional source in summer from photolysis ofnitrogen dioxide. This model simulates very well the observed ozone records,reproducing both the small diurnal cycle in ozone mixing ratio observedduring the summer months, and the factor of two seasonal ozone cycle showinga distinct winter maximum and summer minimum. The model result confirms thatunder the low-NO_x conditions of the clean marine boundarylayer net photochemical loss of ozone occurs at all times of year.     

Baseline atmospheric condensation nuclei at Cape Grim 1977–1987

The meaning of baseline as applied to measurements of CN, at atmospheric monitoring sites such as Cape Grim, is discussed and the idea that a baseline exists only in a statistical sense advocated. Use of the concentration frequency-distribution geometric-mean is proposed as the best measure of CN concentrations. Variations in CN concentrations at Cape Grim for periods greater than 12 months are derived by Kalman filtering the monthly estimates of geometric mean concentration obtained from 1977 to 1987. Significant variations are shown to be present on this timescale with quasi-periodic oscillations in concentration. Some association between major fluctuations and El-Nino Southern Oscillation perturbations in the regional circulation is suggested.     

Cape Grim isotope measurements — A preliminary assessment

Measurements of the stable carbon isotope ratio in atmospheric CO₂ permit a distinction between variations resulting from biospheric and oceanic exchange. In situ extraction of CO₂ from Cape Grim air (41°S) for isotopic analysis commenced in 1977; however difficulties with technique reliability were experienced until 1982. Since 1982, 2.6 years of relatively consistent values have accumulated.For a preliminary assessment of the latter data, estimates of the isotopic behaviour from the global transport and inter-reservoir exchange model of Pearman and Hyson (1985) have been employed. The assessment demonstrates the precision requirements of a carbon isotope monitoring program and the relevance of the isotope measurements as a constraint on parameterization of the model.Clear evidence of the changes due to fossil fuel combustion is seen in the year-to-year differences in ¹³C, with the mean and standard error of the overall trend being –0.025±0.005 yr^-1. A significant seasonal variation in ¹³C is apparent, despite considerable inter-annual variability possibly associated with the 1982/83 ENSO phenomena. The average peak-to-peak amplitude is 0.055±0.014 with a maximum on day 85±15 (approx. 26 March).There is some evidence for a complex seasonal inter-relationship between concentration and isotope ratio, both in the Cape Grim data and in Mook et al. (1983) South Pole data, but with marked differences between the stations, and with both different from the model estimates.In particular, the Cape Grim results suggest that exchange with Southern Hemisphere biosphere is the main contributor to the seasonal variation in isotope ratio at this latitude.     

气溶胶核化清除的化学效应──Ⅱ：动力学参数对云滴化学非均匀性的影响

运用已建立的气溶胶核化清除的物理化学模式，研究了云的动力学因子（如：气块上升速度、夹卷作用）对云滴化学非均匀性的影响。计算结果表明：较强烈的云发展（较大的气块上升速度）可加强由于气溶胶核化和云滴凝结增长造成的云滴化学的非均匀程度。夹卷作用抑制了云的发展，因而减弱了这种非均匀程度。夹卷作用同时也造成总体液态水中Ｓ（ＶＩ）、Ｈ＋等浓度的增加，在Ｓｍａｘ附近可达１个量级。如果考虑气溶胶粒子的夹卷，则可使气块内云滴污染物浓度随云滴大小的变化更加复杂化，如：不仅云滴污染物浓度随云滴大小而变化，即使对于相同大小的云滴之间，其污染物浓度也可相差很大。     

Investigation of droplet dynamics in a convective cloud using a Lagrangian cloud model

A precipitating convective cloud is simulated successfully using the Lagrangian cloud model, in which the flow field is simulated by large eddy simulation and the droplets are treated as Lagrangian particles, and the results are analyzed to investigate precipitation initiation and to examine the parameterization of cloud microphysics. It is found that raindrops appear initially near the cloud top, in which strong turbulence and broadened droplet spectrum are induced by the entrainment of dry air, but high liquid–water mixing ratio is maintained within cloud parts because of insufficient mixing. Statistical analysis of the downward vertical velocity of a droplet W reveals that the transition from cloud droplets to raindrops occurs in the range 20 μm < r < 100 μm, while the variation of W depends on turbulence as well as the droplet radius r. The general pattern of the raindrop size distribution is found to be consistent with the Marshall–Palmer distribution. The precipitation flux can be underestimated substantially, if the terminal velocity $w_{\text{s}}$ is used instead of W, but it is not sensitive to the choice of the critical droplet radius dividing cloud drops and raindrops. It is also found that precipitation starts earlier and becomes stronger if the effect of turbulence is included in the collection kernel.     

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。     

气溶胶浓度对暖云不同生长阶段物理特征影响的模拟研究

基于云微物理过程完善的TAU2D分档云模式, 模拟研究了用热泡扰动生成的暖云在不同气溶胶数浓度(Na)背景条件下各演变阶段云微物理量的变化特征。结果表明: 在暖云的发展过程中Na越高, 云滴尺度变小, 云滴间的碰并增长发动较晚, 云滴谱因碰并增长而实现的滴谱拓宽变弱, 云滴谱相对较窄, 云滴谱标准差较小, 因此云体发展越缓慢, 云体生命周期越长, 形成降水就越晚; 反之, 云滴尺度越大, 碰并增长发动越早, 云滴谱拓宽更明显, 云滴谱标准差越大, 云体生命周期相对更短, 降水开始时刻越早。高Na背景下, 碰并阶段云滴谱较凝结阶段更宽, 沉降阶段因云体下沉蒸发导致小尺度云滴减少, 使其滴谱较碰并阶段略有拓宽。在凝结阶段, 低气溶胶背景下云滴数浓度(N)和离散度(ε)间呈现正相关关系, 而高气溶胶背景下两者为负相关关系。在碰并阶段, N与ε的相关性关系为负相关, 且随着气溶胶数浓度的增加, 负相关程度降低。在沉降阶段, N和ε间为负相关关系。     

夏季硫酸盐和黑碳气溶胶对中国云特性的影响

利用WRF-Chem（Weather Research and Forecasting model coupled with Chemistry）模式研究2006年8月1日—9月1日中国区域硫酸盐和黑碳气溶胶对云特性的影响。模式验证利用了卫星和地面观测的气象要素、化学物质浓度、气溶胶光学特性和云微物理特性。模式性能评估表明该模式能较好地抓住气象要素（温度、降水、相对湿度和风速）的量级和空间分布特征。通过与地面观测和MODIS卫星数据对比发现,尽管模式模拟还存在偏差,但还是能较好模拟出气溶胶物种的地表浓度、气溶胶光学厚度（AOD）、云光学厚度（COD）、云量（CLDF）、云顶云滴有效半径（CER）和云水路径（LWP）。通过两个敏感性试验（分别增加二氧化硫和黑碳排放量至控制试验排放的3倍）与控制试验的对比发现硫酸盐比黑碳更易成为云凝结核,在中国东部云顶云滴数浓度和其它云特性参数对二氧化硫排放增加的响应均从北向南呈递增,这与地面湿度分布有关。云滴有效半径对硫酸盐气溶胶的响应符合气溶胶第一间接效应的定义,即硫酸盐气溶胶增多,云滴数浓度增加,云滴有效半径减少,但是对黑碳气溶胶的响应在各区域不尽相同。还发现黑碳对云量的影响远大于硫酸盐,主要原因是由于黑碳气溶胶直接辐射效应（对太阳光的吸收）导致的云的“燃烧”作用。      

爆炸对云滴碰并增长的实验研究

在2m3云室中进行了一组研究爆炸对云滴碰并增长影响的试验。用一个模拟爆炸源产生冲击波，通过沉降取样和FSSP观测爆炸前后的滴谱变化。沉降取样结果表明，在爆炸声压级130 dB作用后的2分钟内，滴谱变宽，较大云滴浓度增加。从室内试验看，爆炸冲击波似乎能促进云滴的碰并过程。本文结果为爆炸对暖云影响提供了一种可能的解释。     

Cloud optical properties at Bergen (Norway) based on the analysis of long-term solar irradiance records

Summary Ground-based measurements of incoming solar irradiance and cloud observations during a 26 year period (1965–1990) at Bergen, Norway were used in conjunction with a comprehensive radiation model to infer the cloud optical depth under completely overcast conditions.Month-to-month and year-to-year (April through October) statistics of the cloud optical depth and observed cloud forms are presented. Some climate-related features, specifically, diurnal and seasonal variabilities in are examined. The effects of local cloudiness are pointed out and discussed. There appears to be a slight trend towards increasing cloud optical depth at noon during the warm period of the year. The possible uncertainties due to unknown size of cloud droplets are analyzed by model simulations. Possible directions for future research are suggested provided more meteorological and/or satellite information is available.With 9 Figures     

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.     

Adiabatic predictions and observations of cloud droplet spectral broadness

The evolution of cloud droplet size spectra is calculated using an adiabatic condensational growth model. Broadness (e.g., standard deviation of diameter) of cloud droplet spectra in adiabatic cloud parcels was determined to be critically dependent on cloud supersaturation. Although droplet spectra become narrower as growth continues, the rate of narrowing is slower when cloud supersaturation is lower. This actually leads to broader droplet spectra for more continental clouds or for weaker updrafts because both of these conditions are associated with lower cloud supersaturations. More continental type clouds, which have higher concentrations of smaller droplets, were indeed found to have larger dispersions (standard deviation of diameter/mean diameter of cloud droplets). Some of these results were consistent with observations, but the larger dispersions that were much more commonly observed for continental compared to maritime clouds were due almost exclusively to smaller droplets rather than broader droplet distributions. Contrary to the model calculations, typical observations show that cleaner clouds usually have broader droplet spectra. The gaps in magnitude between theory and observations of broadness are significant in all clouds. When cloud parcels that had ascended under different updraft conditions were compared at a constant cloud altitude, parcels with lower updrafts were predicted to have broader droplet spectra with larger mean diameters. This trend of apparent spectral broadening was consistent with observations for some near-adiabatic cloud parcels.     

三参数云微物理方案中气溶胶谱函数对云滴谱影响的数值模拟研究

观测和分档方案的数值模拟都证明气溶胶的谱分布特征对云滴谱的演变有直接影响继而作用于降水的发展。目前广泛使用的总体双参数云滴谱方案因为表征云滴谱的预报量不足,在凝结过程中云滴谱呈不正常的拓宽现象。因此在参数化方案中,气溶胶谱对云滴谱的影响未有明确结论。中科学院大气物理研究所(IAP)云降水物理与强风暴重点实验室(LACS)新研发的三参数方案(IAP-LACS)通过增加的预报量克服了云滴谱的拓宽问题,提高了云滴谱模拟的准确性。为了研究在参数化方案中气溶胶谱分布特征对云滴谱的影响,本文采用新方案进行WRF(Weather Research and Forecasting mode)大涡理想性试验,验证了新方案中气溶胶对数正态谱函数中数浓度、几何半径和标准差3个参量对云滴谱演变的影响。针对3个参量的敏感性试验表明新的气溶胶活化方案和三参数云滴凝结增长方案能够描述气溶胶谱对云滴谱演变的影响规律:气溶胶数浓度对云滴谱影响最显著,数浓度越高活化生成的云滴数量越多,云滴半径越小,云滴谱趋向窄谱,气溶胶数浓度低时,云滴数量少、半径大。较大的几何半径使气溶胶谱向大粒径移动,导致大云滴生成,标准差对云滴谱的影响最不显著。     

Computer modelling of clouds at Kleiner Feldberg

The airflow, cloud microphysics and gas- and aqueous-phase chemistry on Kleiner Feldberg have been modelled for the case study of the evening of 1 November 1990, in order to calculate parameters that are not easily measured in the cloud and thus to aid the interpretation of the GCE experimental data-set. An airflow model has been used to produce the updraught over complex terrain for the cloud model, with some care required to ensure realistic modelling of the strong stable stratification of the atmosphere. An extensive set of measurements has been made self-consistent and used to calculate gas and aerosol input parameters for the model. A typical run of the cloud model has calculated a peak supersaturation of 0.55% which occurs about 20 s after entering cloud where the updraught is 0.6 m s^–1. This figure has been used to calculate the efficiency with which aerosol particles were scavenged; it is higher than that calculated by other methods, and produces a cloud with slightly too many droplets. A broad cloud droplet size spectrum has been produced by varying the model inputs to simulate turbulent mixing and fluctuations in cloud parameters in space and time, and the ability of mixing processes near cloud-base to produce a lower peak supersaturation is discussed. The scavenging of soluble gases by cloud droplets has been observed and departures from Henry's Law in bulk cloud-water samples seen to be caused by variation of pH across the droplet spectrum and the inability of diffusion to adjust initial distributions of highly soluble substances across the spectrum in the time available. Aqueous-phase chemistry has been found to play a minor role in the cloud as modelled, but circumstances in which these processes would be more important are identified.     

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.     

Aerosol-cloud chemical fractionation: Enrichment factor analysis of cloud water

A field study was conducted at a mountain-top site in northwestern Colorado. Supercooled cloud water, collected as a function of droplet size, was analyzed for anions, cations and trace elements. Enrichment factors (EF) of SO ₄ ^2– , K⁺, Na⁺ and Cl^– relative to crustal and marine reference elements (Al and Na) were calculated to determine whether chemical fractionation of the aerosol occurs during cloud droplet formation. The largest EF's for all ions were found for droplets less than 10–15 µm diameter. Ratios of the small to large droplet mean EF's ranged from 1 to 2, for SO ₄ ^2– relative to both Al and Na⁺, to 10 to 12 for Na⁺, Cl^– and K⁺, relative to Al. EF's of K⁺ and Cl^– in the bulk cloud water were in crustal and marine proportions, respectively. It was concluded that although bulk could chemistry may indicate a lack of enrichment of a species, this may not be true throughout the droplet size distribution. The higher enrichments in small droplets is likely a result of their formation on small aerosol particles whereas the large droplets form on the largest aerosol particles. This may suppress EF's in precipitation relative to the total aerosol.     

海洋层积云中的云滴谱宽度及其影响因子

云滴谱宽度对模式中云的光学厚度的参数化、气溶胶间接效应的评估以及降水形成过程的研究至关重要。本文利用美国POST（Physics of Stratocumulus Top）项目2008年7月19日的飞机观测资料，分析了微物理量和云滴谱的垂直分布及微物理过程。结果表明，该云系云滴谱宽度在云底附近较大，这是由低层核化过程导致的；中层凝结增长过程使得云滴谱宽度随高度增加逐渐减小；云顶附近夹卷混合过程导致云滴谱宽度增大。绝热云中垂直速度的增大会促进云凝结核的活化使云滴数浓度增大，促进凝结增长使云滴尺度增大、云滴谱宽度减小，云滴谱宽度与云滴数浓度、云滴尺度呈现负相关关系；云洞中受夹卷混合过程影响，垂直速度减小，云滴蒸发，云滴数浓度和云滴尺度减小、云滴谱宽度增大，且该效应随绝热程度减小而增强。建议云滴谱宽度的参数化将垂直速度、云滴数浓度、云滴尺度和绝热程度等考虑在内。