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.     

Wet deposition of radionuclides derived from the Chernobyl accident

Chernobyl radioactivity in precipitation was measured at Tsukuba, Japan, as were both surface-air concentrations and particle-size distributions of Chernobyl-released radionuclides. To understand the wet removal processes of the Chernobyl radionuclides, i.e.¹³⁷Cs,¹⁰³Ru, and⁹⁰Sr, wet deposition velocities were calculated. The wet deposition velocities of the Chernobyl radioactivity for individual rainfall events varied largely. The wet deposition velocity is given as the product of washout ratio and rainfall rate. Typically, it was found that the washout ratios of⁹⁰Sr are systematically larger than those of¹³⁷Cs. In order to explain this fact, we examined the relationship between the washout ratios and particle sizes of radionuclide-bearing aerosols. A positive correlation between corrected washout ratios and particle size was found with a particle diameter range from 0.35 to 1.2 µm. The result strongly suggests that the factors controlling the wet removal of the Chernobyl radioactivity for individual rainfall events are surface air concentration, particle size, and rainfall rate, rather than precipitation amount, which is in agreement with previous understandings. This suggests that high contamination areas of radioactivity are formed during heavy rainfall events with high rainfall rates in the case of tropospheric injection such as the Chernobyl accident.     

The chemical fractionation of atmospheric aerosol as a result of snow crystal formation and growth

The relationships between the physical and chemical properties of mixed-phase clouds were investigated at Storm Peak Laboratory (3220m MSL) located near the continental divide in northwestern Colorado. Interstitial aerosol particles, cloud droplets and snow crystals were concurrently collected when the laboratory was enveloped by a precipitating cloud. All samples were analyzed for trace elements, soluble anions, electrical conductivity and acidity.The results show average trace constituent concentration ratios of cloud water to snow water range from 0.4 to 26. All but six of the 32 elements and ions measured had ratios greater than one. This result suggests a chemical species dependency of in-cloud aerosol particle scavenging processes. Evidence of a decrease of in-cloud aerosol particle scavenging efficiency by snow due to increases in aerosol concentration is also presented.Differences between the chemical composition of cloud water and snow water are manifested most strongly when snow crystals grow by vapor deposition. In-cloud scavenging efficiencies by snow crystals for most aerosol particle chemical species are dependent on the growth of the snow crystals by accretion of cloud droplets. This chemical fractionation of the atmospheric aerosol by snow crystal formation and growth should be most active where narrow, continental cloud droplet size distributions and low liquid water contents are prevalent, enhancing the probability of snow crystal growth by diffusion.     

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.     

On the scavenging of gaseous nitrogen compounds by large and small rain drops: II. Wind tunnel and theoretical studies of the simultaneous uptake of NH3, SO2 and CO2 by water drops

An experimental investigation of the simultaneous absorption of NH₃ and SO₂ from the ambient atmosphere by freely falling water drops has been carried out in the Mainz vertical wind tunnel. The experimental results were found to be in good agreement with the results derived from computations with the Kronig-Brink convective diffusion model and also with a model which assumes a drop to be well mixed at all times. Encouraged by this agreement, these computation schemes for the uptake of gas by single drops where incorporated in a pollution washout model with realistic SO₂, NH₃ and CO₂ gas profiles. This model allows an entire raindrop size distribution to fall through a gas layer. The results of this plume-model show that the SO₂ uptake is strongly dependent on the NH₃ concentration in the atmosphere and on the rainrate. We also find that the small drops contribute more towards the washout of these gases. In the case of simultaneous presence of NH₃ and SO₂, desorption of these gases is negligible.     

The characterization and distribution of aerosol and gaseous species in the winter monsoon over the western pacific ocean

During the winters of 1981 and 1982, measurements were taken on two Japanese islands of the aerosol and gaseous species which had been carried by northwesterly monsoons over the Pacific Ocean. The aerosols were characterized as sea-salt particles; soil particles, and as particles of sulfate, nitrate, organics and elemental carbon. At Chichi-jima island, which is about 800 km away from the main islands of Japan, it was found that the level of the anthropogenic components of the aerosols was considerably higher than their background level. The mean concentrations of the species on the islands are given in tabular forms. According to a survey made on board a ferry boat, the aerosol and gaseous species were fairly uniformly distributed along the southern coast of the main Japanese islands.     

The characterization and distribution of aerosol and gaseous species in the winter monsoon over the western pacific ocean

In order to obtain a better understanding of the behavior of aerosols and SO₂ in the longrange transport through a marine boundary layer, a simple box-model is applied to the evaluation of the residence times of the species from the concentrations of gases and aerosols measured simulataneously on two islands in the West Pacific Ocean in the north-west monsoon. For Aitken and large particles, the residence time is varied from 3.7 to 7.4 days depending on the particle size, and their flux to the sea is equal to or slightly smaller than that of the free atmosphere. The residence time of giant particles is about one day and their flux to the sea is three times larger than that of the free atmosphere. The residence time of SO₂ is 15 hr, and the relative SO₂ mass flows of the deposition to the sea, of the diffusion to the free atmosphere and of the transformation to SO₄ ^2- are approximately 4, 1 and 1, respectively.     

On the scavenging of organic gases by cloud and raindrops: I. A theoretical and experimental study of acetaldehyde absorption and desorption for water drops in air

Our previously developed theoretical models for describing the rate at which water-soluble atmospheric trace gases are scavenged by cloud and rindrops were evaluated for the case of acetaldehyde being absorbed and desorbed by water drops of radii between 250 to 2500 m radius. The experimental verification of our theoretical predictions was carried out in the UCLA 33 m high precipitation shaft in which falling water drops were allowed to come to terminal velocity before passing through a chamber of variable lengths filled with air containing acetaldehyde at various partial pressures. For all drop sizes studied, the experimental results and the theoretical predictions were in reasonable agreement.     

On the scavenging of gaseous nitrogen compounds by large and small rain drops I. A wind tunnel and theoretical study of the uptake and desorption of NH3 in the presence of CO2

An experimental study has been carried out in the Mainz vertical wind tunnel to determine the rate at which NH₃ in the presence of CO₂ is absorbed by freely suspended water drops. The experimental uptake rates were found to be in good agreement with the rates predicted by the Kronig-Brink convective diffusion model and, for gas concentrations in the ppbv range also by the model in which it is assumed that the absorbed gas is well mixed inside the drop (henceforth called well mixed model). The same conclusion was shown to apply also to the desorption of NH₃ from a drop previously exposed to NH₃. The latter result is in contrast to the desorption of SO₂ which must be described by a model which accounts for the diffusion of the species inside the drop. Comparison of our experimental results with theory show further that the uptake of NH₃ in presence of CO₂ is significantly overestimated if the slow reaction CO_2(aq)+H₂OHCO ₃ ^– +H⁺ is neglected in the theoretical computation.     

湿静力平衡温度及其在大气对流运动中的应用

提出了一个新的大气动力-热力学温湿参量——湿静力平衡温度（T_s）。它与密度温度（T_ρ）有密切关系。作为T_s的应用示例,简化了积云一维时变模式垂直运动方程;提出了“载水气块”和“非载水气块”统一的新的“对流有效位能”表达式。结合实例,计算了“载水气块”和“非载水气块”两种情况下的对流有效位能（分别记作CAPE_w和CAPE）以及对流抑制能量（分别记作CIN_w和CIN）等,“载水气块”与“非载水气块”两种情况的“对流有效位能”及“对流抑制能量”有较大差异。作为强对流天气分析预报的重要参数,目前计算对流有效位能和对流抑制能量的通用公式存在一定缺陷;在对“对流有效位能”的理解方面存在某些模糊认识和盲点。从新的观察角度对“对流有效位能”的概念做了详细分析并进一步阐明了其确切含义。新的方案同样可以方便地在T-lnp图上进行稳定度分析,并可根据新的公式对T-lnp的某些缺点进行修正。     

The measurement of natural sulfur emissions from soils and vegetation: Three sites in the Eastern United States revisited

Sulfur fluxes from bare soils, naturally vegetated surfaces and from several agricultural crops were measured at two mid-continent sites (Ames, Iowa and Celeryville, Ohio) and from one salt water marsh site (Cedar Island, North Carolina) during a field program conducted jointly by the NOAA Aeronomy Laboratory, Washington State University Laboratory for Atmospheric Research and University of Idaho Department of Chemistry during July and August 1985. The sites were chosen specifically because they had been characterized by previous studies (Anejaet al., 1979; Adamset al., 1980, 1981). The NOAA gas chromatographic/dynamic-enclosure measurements yielded bare soil surfaces fluxes from the mid-continent sites composed predominantly of COS, H₂S, CH₃–S–CH₃ (DMS) and CS₂, all of which were strongly correlated with air temperature. Net fluxes of approximately 5 and 15 ng S/m² min were observed in Iowa and Ohio, respectively, at appropriate weighted mean July temperatures. These fluxes are roughly a factor of 10 smaller than the earlier measurements, the greatest difference being in the measurement of the H₂S flux. The presence of growing vegetation was observed to measurably increase the flux of H₂S, significantly increase that of DMS and to decrease that of COS. Sulfur fluxes in the Cedar Island environs were observed to be both spatially and temporally much more variable and to include CH₃SH as a measurable contributor. Net fluxes, composed predominantly of DMS and H₂S, were estimated to be about 300 ngS/m²min during August; again about a factor of 10 lower than previous estimates. All measurements were corroborated to within about a factor of 2 by those of the other participating laboratories.     

The effect of nitrogen fertilization on the COS and CS2 emissions from temperature forest soils

The net fluxes of carbonyl sulfide (COS) and carbon disulfide (CS₂) to the atmosphere from nitrogen amended and unamended deciduous and coniferous forest soils were measured during the spring of 1986. We found that emissions of these gases from acidic forest soils were substantially increased after nitrogen fertilization. The total (COS+CS₂) emissions were increased by nearly a factor of three in the hardwood stand and were more than doubled in the pine stand. Furthermore, vegetation type appeared to have an influence on which was the dominant sulfur gas released from the forest soils. The added nitrogen caused a dramatic increase in COS emissions from the hardwood stand (a factor of three increase), while CS₂ emissions from this site were not affected. We observed the opposite response in the pine stand; that is, the nitrogen fertilization had no affect on COS emissions, but did stimulate CS₂ emissions (a factor of more than nine increase).     

On the scavenging of SO2 by cloud and raindrops: I. A theoretical study of SO2 absorption and desorption for water drops in air

An extention of our previous theory for trace gas absorption into freely-falling cloud and raindrops is presented. This theory describes the convective diffusion of a trace gas through air and into a water drop with internal circulation, the drop falling at its terminal velocity. Using flow fields for the circulating water inside and for the moving air outside the drop, obtained by numerical solutions to the Navier—Stokes equation of motion, we numerically solved the convective diffusion equation to determine the uptake of SO₂ by water drops of various sizes, time exposure to the gas phase, and concentration of SO₂ in the gas phase. It was found that for drops of radius larger than 1 mm and relatively low gas concentrations (10 ppb (v)), resistance to gas diffusion lies mainly in the gas phase; while for drops of radius less than 500 m and gas concentrations larger than those found in the atmosphere (1% (v)), the resistance to diffusion lies primarily in the liquid phase. With drop sizes and gas concentrations between these limits, the rate of SO₂ uptake is controlled by a coupled resistance to diffusion inside and outside the drop. In addition to our general model, a simplified version was formulated which allows considerable savings in computer time for evaluation and improved ease of handling without significant loss of accuracy. A comparison between our simplified model and that of Barrie (1978) shows that the boundary-layer approach of Barrie may be a useful alternate approach to estimating trace gas absorption by water drops, provided appropriate values are chosen for the thickness of the boundary layers involved.     

On the scavenging of SO2 by cloud and raindrops: II. An experimental study of SO2 absorption and desorption for water drops in air

For the purpose of testing our previously described theory of SO₂ scavenging a laboratory investigation was carried out in the UCLA 33 m long rainshaft. Drops with radii between 250 and 2500 m were allowed to come to terminal velocity, after which they passed through a chamber of variable length filled with various SO₂ concentrations in air. After falling through a gas separating chamber consisting of a fluorocarbon gas the drops were collected and analyzed for their total S content in order to determine the rate of SO ₂ absorption.The SO₂ concentration in air studied ranged between 1 and 60% (v). Such relatively large concentrations were necessary due to the short times the drops were exposed to SO₂ in the present setup. The present experimental results were therefore not used to simulate atmospheric conditions but rather to test our previously derived theory which is applicable to any laboratory or atmospheric condition. Comparison of our studies with the results from our theory applied to our laboratory conditions led to predicted values for the S concentration in the drops which agreed well with those observed if the drops had radii smaller than 500 m. In order to obtain agreement between predicted and observed S concentrations in larger drops, an empirically derived eddy diffusivity for SO₂ in water had to be included in the theory to take into account the effect of turbulent mixing inside such large drops.In a subsequent set of experiments, drops initially saturated with S (IV) were allowed to fall through S-free air to determine the rate of SO ₂ desorption. The results of these studies also agreed well with the results of our theoretical model, thus justifying the reversibility assumption made in our theoretical models.In a final set of experiments, the effects of oxidation on SO₂ absorption was studied by means of drops containing various amounts of H₂O₂. For comparable exposure times to SO₂, the S concentration in drops with H₂O₂ was found to be up to 10 times higher than the concentration in drops in which no oxidation occurred.     

1961—2010年东北地区夏季降水时空变化的研究

东北地区地处中高纬欧亚大陆东岸,处在东亚季风区的边缘,其降水主要集中在夏季,并且降水量具有显著的地域差异和年际变化。研究东北夏季降水特点,可为降水预报、气候预测和农业生产提供可靠依据。本文利用东北地区27个测站1961—2010年夏季逐月降水资料,通过E-OF和小波分析的方法研究东北地区夏季降水的时空变化规律,结果表明：东北地区夏季降水量主要表现为三种空间分布型：总体一致型、南-北反位相型以及东南-西北反位相型;东北地区夏季降水量存在明显的年际变化,降水变化周期为8—11a;东北地区夏季各月降水量的差异,主要是由地形原因和纬线跨度差异造成的。     

On the scavenging of SO2 by large and small rain drops: V. A wind tunnel and theoretical study of the desorption of SO2 from water drops containing S(IV)

An experimental and theoretical study has been carried out to investigate the rate of desorption of SO₂ from water drops falling at terminal velocity in air. The experiments were carried out in the Mainz vertical wind tunnel in which water drops of various sizes containing S(IV) in various concentrations were freely suspended in the vertical airstream of the tunnel. The results of these experiments were compared with the predictions of three theoretical models, and with the experiments of Walceket al. This comparison shows that the predictions of the diffusion model of Kronig and Brink in the formulation given by Walcek and Pruppacher agree well with the experimental results for all relevant large and small rain-drop sizes, and for all considered concentrations of S(IV) inside the drops. In contrast, the predictions of the diffusion model which assumes complete internal mixing inside a drop agrees with the experimental results only if the concentration of S(IV) inside the drop is less than that equivalent of an equilibrium SO₂ concentration of 15 ppbv. At larger concentrations, the theoretical predictions of the model for complete internal mixing progressively deviate from the experimental results. It is further shown that Barrie's double film model can be used to interpret the resistance to diffusion inside a drop in terms of a diffusion boundary layer inside the drop which increases in thickness with decreasing concentration of S(IV). Applying our results to the desorption of SO₂ from small and large rain drops falling below an assumed cloud base, shows that for typical contents of S(IV) inside the drops substantial amounts of SO₂ will desorb from these drops unless H₂O₂ is present in the surrounding air.     

中高纬度与热带大气的共同作用对江南4-6月低频降水的影响

基于中国国家气象观测站的逐日降水资料、NOAA (National Oceanic and Atmospheric Administration)提供的逐日向外长波辐射资料和NCEP(National Centers for Environmental Prediction)/NCAR(National Center for Atmospheric Research)逐日全球再分析资料,采用非滤波法提取10-30 d低频降水及低频环流因子,分析了1979-2013年江南地区4-6月低频降水及其关联的大气环流特征,着重讨论了中高纬度与热带共同作用对低频降水的影响及可能机理。结果表明:(1)江南4-6月降水的第1模态呈现全区一致的变化趋势,其10-30 d低频降水方差贡献率在江南南部较大,部分区域可达20%。(2)降水的低频异常不仅与热带对流有关,还与中高纬度大气环流的变化显著相关。当东印度洋及印度尼西亚一带对流旺盛,中国上游欧洲至西伯利亚地区高纬度位势高度表现为显著的正异常,江南上空为负异常时,有利于江南低频降水。(3)中高纬度大气环流与热带对流共同作用影响江南4-6月低频降水:当热带对流旺盛区(抑制区)位于东印度洋及印度尼西亚海洋性大陆一带时,热带热源的非绝热加热引起显著的上升(下沉)运动,并激发经向罗斯贝波北传;同时高纬度欧洲至西伯利亚地区的位势高度负异常(正异常)向东向南传播,两者在江南上游叠加,低压(高压)底前部的西南风(东北风)有利于孟加拉湾对江南的水汽输送加强(减弱),对应江南地区整层水汽通量辐合(辐散),低频降水偏多(偏少)。     

1981－2020年沂沭河流域极端降水事件特征及环流背景

利用1981—2020年沂沭河流域内12个气象台站逐日降水观测资料,西太平洋副热带高压（西太副高）指数、太平洋年代际振荡指数（PDO）等资料以及NCEP/NCAR逐日再分析资料,采用线性趋势分析、累积距平法联合滑动t检验、morlet小波分析、相关性分析、合成分析等方法,研究近40 a沂沭河流域极端降水事件的时空变化特征,并进一步研究极端降水指数与气候因子之间的相关性以及极端降水事件的异常环流背景。结果表明：沂沭河流域极端降水事件具有整体上增多且强度增强的特征,且近年来在频次和年极端降水量上波动峰间值增大,分别为6.2 d/a、538.2 mm/a,极端降水事件日趋严重。空间分布上南多北少,中部、北部较南部增速更明显。极端降水频次和年极端降水量均在1989年和2002年左右突增;极端降水强度在1989年突增,2000年左右突减。极端降水的频次、强度和年极端降水量分别以22 a、10 a和22 a的周期波动为主。西太副高的脊线位置跟频次和年极端降水量具有正相关性,PDO与频次和年极端降水量具有负相关性。东亚夏季风强度和西太副高的位置是影响沂沭河流域极端降水事件多寡的重要因子,在预测该流域的极端降水情况时可做参考依据。     

藏北高原土壤温、湿度变化在高原干湿季转换中的作用

通过1997年和1999年藏北高原沱沱河观测站土壤温、湿度变化和对应降水变化的分析,表明与高原冻融过程相联系的土壤湿度变化和高原干湿季转换及湿季降水存在联系。土壤融冻引起土壤增湿的时间比高原雨季降水开始的时间约早20天,春季高原土壤温、湿度的增加在高原地表感潜热的变化中有重要贡献。春末夏初高原土壤冻融过程引起的土壤湿度变化,在高原局地尺度的水分循环中为高原湿季开始提供了有利的水汽条件。因此,在青藏高原陆气相互作用过程中,与冻融过程相联系的土壤湿度变化在高原季节转换中是一个不可忽视的因子。