Atmospheric residence times for soluble species: Differences in numerical and analytical model results

We have compared numerically calculated soluble species residence times with several analytic residence time models. The numerical results are dependent on whether randomly or periodically distributed precipitation events are assumed. A preferred time of occurrence for rain, such as morning or afternoon, influences the computed HNO₃ residence time for precipitation cycle times (wet plus dry period) of about a day, but exerts less influence as the cycle time increases. An analytic residence time model developed by Rodhe and Grandell (1972, Tellus24, 442–454) is found to agree well with residence times computed for randomly distributed precipitation events while a model developed by Giorgi and Chameides (1985, J. geophys. Res.90, 7872–7880 is more suitable for periodic rain. The present numerical calculations resolve an apparent ambiguity in HNO₃ residence times computed in earlier numerical studies.Using mean precipitation periods and rainfall amounts characteristic of the northeastern U.S. as a guide, we find that residence times computed under the assumption of randomly distributed wet and dry events agree better with observed aerosol lifetimes than do those computed assuming periodic rain.     

Acid rain model development considering altitudinal precipitation rate

A one-dimensional Eulerian model is developed to investigate the effect of physico-chemical parameters on the acidification processes of raindrops. The model is structured to treat the complex cloud's microphysical processes in a highly parameterized fashion. For a 1 h rain event simulation, gas depletion ratios range from 35 to 60%, 40 to 70%, and 25 to 30% for HNO₃, NH₃ and SO₂, respectively. Also, a formula is proposed to predict the rain acidity on the ground using known values of gaseous SO₂ concentration, the height of the rain growth zone, and precipitation rate.     

Numerical modeling of long-range transport of acidic species in association with mesoβ-convective-clouds across the Japan sea resulting in acid snow over coastal Japan—II. Results and discussion

The acid snow/rain model [describedin Part I, Kitada et al., Atmospheric Environment27A, 1061–1076, 1993] was applied to investigate transport/transformation/deposition of acidic species in association with snow-precipitating cloud over the Japan Sea in winter. The model results showed: (1) The snow-precipitating clouds generated by relatively weak convective motions tend to trap aerosols of sulfate and nitrate and soluble gases such as SO₂ and HNO₃ below cloud levels, thus keeping their concentrations at higher levels than those for no-cloud situations. The mechanisms involved are: transfer of gas- and aerosol-phase species to cloud-phase through absorption and nucleation scavenging, then their transfer from cloud to snow through riming, and subsequent release from sublimating snow back to gas- and aerosol-phases below cloud base. (2) In-cloud oxidation enhanced the overall conversion of SO₂ to SO₄²⁻ by some 25% with respect to no-cloud situation after 12 h. Furthermore, contributions to the oxidation were 77.4%, 21.1% and 1.5% for S(IV)H₂O₂, S(IV)O₂ with catalysts of Fe³⁺ + Mn²⁺ and S(IV)O₃ reactions, respectively. (3) The sulfate wet deposited by precipitating snow for 12 h was due mostly to in-cloud scavenging and in-cloud oxidation, i.e. 66% by nucleation scavenging and the remaining by in-cloud oxidation of S(IV), while the contribution of below-cloud scavenging was negligible. (4) The adsorption process of HNO₃ onto the surface of falling snow was found to account for major below-cloud scavenging of snow, and thus in contrast to SO₄²⁻, the below-cloud scavenging contributed very significantly to the nitrate wet deposition. Throughout the stimulation, below-cloud scavenging was responsible for 75% of the snow-NO₃⁻ formation. Therefore, taking account of this process in acid snow models is important.     

Parameterization of episodical cloud and rainout events in large-scale atmospheric chemistry models

A parameterization scheme taking into account the episodical nature of rainout and incloud chemical transformation has been tested in a 2-D channel model. In the liquid phase many soluble gases are observed in concentrations never experienced in the gas phase. The effects on the trace gases SO₂ and hydrogen peroxide, when they are modified by clouds and precipitation, are studied. When incloud interaction of SO₂ and hydrogen peroxide is taken into consideration, calculated hydrogen peroxide profiles are brought closer to observed distributions. The effect of varying the time periods between cloud and rain events is tested. The impact on the formation and destruction of tropospheric ozone is also discussed.     

酸雨对两广地区农作物的经济损失研究

本研究通过模拟试验和现场调查,确立两广地区主要农作物对酸性降水、SO₂单一污染,酸性降水与SO₂复合污染的产量反应生态基准值。根据酸性降水年均pH和SO₂年日均浓度等值线,农作物的空间分布,采用市场价格法,估算了酸雨引起两广地区农作物经济损失值。      

Numerical simulation of wet scavenging of air pollutants—II. Modeling of rain composition at the ground

The modeling of rain composition for a convective shower (Tucson, AZ, 10 September 1977) and a frontal precipitation event (Den Helder, Holland, 12 December 1978) is performed in this paper by including the pollutant species and wet scavenging mechanisms into the mass transport equation of the sequential sampling model described in Part I of this series. The results indicate that: (1) the major scavenging mechanisms of most pollutants in convective showers appear to be similar to those in frontal precipitations; (2) the major scavenging mechanisms of NH₄ and NO₃ are gas absorption, whereas the absorption of SO₂ by aqueous drops and oxidation of S(IV) by H₂O₂ and O₃ in the aqueous phase are the major formation and scavenging mechanisms for SO₄; (3) the scavenging by raindrops in the below-cloud region is the dominant removal mechanism for coarse particles, whereas nucleation is the major scavenging mechanism for submicrometer particles; (4) H₂O₂ is the most important oxidant responsible for the oxidation of S(IV) and the formation of sulfate in precipitation; (5) the contributions of both (SO₂ + H₂O₂) and (SO₂ + O₃) reactions to sulfate concentration in precipitation are larger for convective precipitation than for frontal precipitation.     

A denuder technique for the measurement of nitrous acid in urban atmospheres

A new denuder set-up for the measurement of nitrous acid in polluted atmospheres is described here. The set-up is composed of one tetrachloromercurate-coated denuder for the removal of SO₂ and two downstream sodium carbonate-coated denuders for the determination of nitrous acid by the differential technique [Febo et al., 19, 1517–1530 1990]. The removal of SO₂ is necessary in order to avoid the formation of artifact nitrite on the sulfite layer which results from the interaction between atmospheric SO₂ and the Na₂CO₃ coating. Because of this mechanism, the measurement of HONO by means of the previously used NaClNa₂CO₃Na₂CO₃ denuder set-up is heavily biased in all cases when SO₂ and NO₂ are present at high concentration levels (e.g. urban environments).     

浙江宁波天童地区酸性降水化学特征研究

为了解浙江宁波天童地区降水的化学特征、离子来源及酸性降水的成因,于2010年3月—2011年2月在该地区采集了90个降水样品,并运用离子色谱法分析其化学组分.结果显示,天童地区降水的酸化频率和酸化程度非常高,酸雨频率为97%,雨量加权pH平均值为4.37,离子浓度的大小顺序为SO24->NH4+>NO3->Ca2+>Cl->Na+>Mg2+>K+>F-,降水较清洁;降水pH值和各离子含量存在明显的季节变化,总体表现为冬、春季污染程度高于夏、秋季;SO24-/NO3-的浓度比值为1.9,表明该地区酸雨类型为硫酸和硝酸复合型;SO24-、NO3-、NH4+和部分Ca2+主要来自人为污染源,Na+、Cl-和大部分Mg2+主要来自海洋源,K+和大部分Ca2+则主要来自地壳源,海洋对天童地区降水离子组分影响较大,但对降水酸度影响并不显著;NH4+与SO42-(r=0.90)、NO3-(r=0.88)的相关性分别大于Ca2+与SO24-(r=0.67)、NO3-(r=0.73)的相关性,且NH4+/Ca2+的浓度比值为1.47,说明NH4+对降水酸性的中和作用大于Ca2+,与我国其他城市降水相比,天童地区降水中的碱性离子,尤其是Ca2+浓度较低,从而导致降水酸度高于北方地区和西南其他地区.     

不同植被下森林地表系统水相硫的分布与迁移

为了阐明酸雨对森林生态系统水相硫动态分布的影响,在1997~1999年以庐山植物园的针叶林和阔叶林为研究对象,对降雨、透冠水、干流水、渗漏水、径流水及硫通量进行了监测分析。结果表明,降水中SO2-4含量最高值出现在冬季,最低值在夏季;针叶林和阔叶林的透冠水、干流水和渗漏水中的SO2-4含量均高于降水,且透冠水和干流水均表现为春夏季较低、秋冬季较高,径流水变化与之相反;渗漏水针叶林冬季最高,阔叶林春季最高,其他三个季节差异不大;森林生态系统水相硫年际变化呈递增趋势,即1997年1998年1999年,1999年SO2-4浓度与1998和1997年之间差异达显著或极显著水平,而1997年和1998年差异不显著;针叶林的透冠水、干流水、渗漏水中的SO2-4含量均比阔叶林高,而径流水则比阔叶林低,其pH值变化与之相反。针叶林和阔叶林都能够较好的吸收大气沉降中的S,其固定量均高于降水中S的通量,故庐山森林生态系统目前仍是大气S沉降的汇,对酸沉降仍有缓冲作用,但针叶林由于高输入低输出,因此对S的固定能力更强。     

成都市降水对大气污染物的清除效果分析

成都市受特殊地形和气候条件影响,地面风速小,静风比例高,空气湿度大,大气污染物扩散缓慢,主要靠降水的冲刷和清除作用去除大气污染物.利用2014年5月13日-2017年12月31日成都市逐小时ρ（PM_2.5）、ρ（PM₁₀）、ρ（NO₂）、ρ（O₃）、ρ（CO）、ρ（SO₂）监测数据和同期地面降水量观测数据,分析了降水前污染物质量浓度、小时最大降水量、降水持续时间及累积降水量对大气污染物清除效果的影响.结果表明:①降水对6种大气污染物的清除率随降水前污染物质量浓度的增加而增大,并且汛期降水对大气污染物的清除率大于非汛期降水.②降水对大气污染物起正清除作用,清除率随降水持续时间的增加而增大.③不同降水量对不同污染物的清除效果不同,对PM_2.5、PM₁₀、NO₂、CO和SO₂的清除率随降水量的增加而逐渐增大,对O₃的清除效果相差不大且清除率均较大;小时最大降水量对PM_2.5、PM₁₀、NO₂、O₃、CO、SO₂的清除率平均值分别为29.48%、26.95%、22.02%、26.87%、11.94%、28.75%,累积降水量的清除率平均值分别为31.64%、30.66%、24.38%、26.31%、13.89%、32.91%,其中CO不易溶于水,降水对其清除作用明显小于其他几种污染物.研究显示,降水对大气污染物的清除作用显著,对SO₂、PM_2.5和PM₁₀的清除效果较好,而对CO的清除效果较差.      

A numerical simulation of the chemistry of a rainband

Comparisons between the observations of a rainband and the results of a numerical simulation with a two-dimensional dynamical chemical model are presented. The simulation produced sulphate concentrations in the precipitation that agreed reasonably well with the observations, which suggests that the treatment of the major pathways for sulphate in the rain is satisfactory. Oxidation within the cloud was found to be a relatively unimportant pathway for this particular precipitation system, the two most important sources of sulphate in the rain being nucleation of sulphate aerosol and washout.     

Studying high ozone concentrations by using the Danish Eulerian model

The long-range transport of air pollutants (LRTAP) over Europe is studied by a mathematical model based on a system of partial differential equations (PDEs). The number of PDEs is equal to the number of species studied and the model contains 35 species at present. Among the species are NO, NO₂, NO₃⁻, HNO₃, NH₃, NH₄⁺, O₃, PAN, SO₂, SO₄²⁻ and may hydrocarbons. Most of the 70 chemical reactions involved in the model are nonlinear (including here many photochemical reactions).The model requires large sets of input data. Emissions of SO₂, NO_x, NH₃ and both natural and anthropogenic volatile organic compounds (VOC) are needed in the model. The meteorological data consist of fields of wind velocities, precipitation, surface temperatures, temperatures of the boundary layer, relative humidities and cloud cover, which are read in the beginning of every 6-h interval. Both daytime and nighttime mixing heights are used in the model.Many of the species in the model vary on a diurnal basis. An investigation of the main mechanisms that determine the diurnal variation of the ozone concentrations is performed. One of the important conditions that is necessary if one wants to represent correctly the diurnal variations of the concentrations is to have access to meteorological data that vary diurnally. This is especially true for the temperature and the mixing height.The use of modern numerical algorithms (which are combined with vectorization of the most time-consuming numerical procedures) allows one to perform long-term runs with the model on several high-speed computers. Results obtained in runs with meteorological data for July 1985 and August–October 1989 are discussed. The computed concentrations and depositions are compared with measurements taken at stations located in different European countries. The agreement between calculated concentrations and measurements is reasonably good.Results obtained with several scenarios, in which the NO_x emission and/or the anthropogenic VOC emissions are varied, are presented. Several main conclusions are drawn by studying the results obtained during the comparisons. Some plans for future development of the models are discussed.     

Origin of soluble chemical species in bulk precipitation collected in Tokyo,Japan: Statistical evaluation of source materials

An iterative least-squares method with a receptor model was applied to the analytical data of the precipitation samples collected at 23 points in the suburban area of Tokyo, and the number and composition of the source materials were determined. Thirty-nine monthly bulk precipitation samples were collected in the spring and summer of 1987 from the hilly and mountainous area of Tokyo and analyzed for Na⁺, K⁺, NH₄⁺, Mg²⁺, Ca²⁺, F⁻, Cl⁻, Br⁻, NO₃⁻ and SO₄²⁻ by atomic absorption spectrometry and ion chromatography. The pH of the samples was also measured. A multivariate ion balance approach (Tsurumi, 1982, Anal. Chim. Acta138, 177–182) showed that the solutes in the precipitation were derived from just three major sources; sea salt, acid substance (a mixture of 53% HNO₃, 39% H₂SO₄ and 8% HCl in equivalent) and CaSO₄. The contributions of each source to the precipitation were calculated for every sampling site. Variations of the contributions with the distance from the coast were also discussed.     

Cloud chemistry at Mt Rigi,Switzerland: Dependence on drop size and relationship to precipitation chemistry

The chemical composition of winter and spring cloud water sampled at 1620 masl elevation on Mt Rigi in central Switzerland was dominated by NO₃⁻, SO₄²⁻, NH₄⁺ and H⁺. A wide range of concentration levels was observed, with maxima of 3700, 1800 and 4600 micronormal for NO₃⁻, SO₄²⁻ and NH₄⁺, respectively. Concentrations at a lower elevation (1030 masl) site on the mountain were higher due to lower cloud liquid water contents and higher pollutant levels at that site. The lowest pH observed was 2.95; large concentrations of NH₃ in the region prevented pH values from falling even lower. A comparison of simultaneously sampled cloud water and precipitation revealed much higher concentrations for most species in the cloud water, except in one case of extreme precipitation riming when the concentrations in the two phases converged. An exception to the pattern was H⁺; at times the precipitation was more acidic than the cloud water. The chemical composition of the cloud drops varied with drop size. Drops smaller than 10 μm diameter were enriched in NO₃⁻, SO₄²⁻ and NH₄⁺ relative to larger drops. Since the larger drops are the ones most effeciently captured by snow crystals, knowledge of their composition is essential to understanding the chemical implications of accretional growth of precipitation.     

西南地区酸雨形成大气化学过程

通过野外观测、实验室实验和数值模拟研究了西南地区酸雨形成大气化学过程.新认识如下:①人为排放引起的酸雨及空气污染,目前尚未明显波及到西藏高原;②在重污染区SO_2污染严重,不管降水云是否酸性或污染,降水总是酸性、受污染的,云下洗脱痕量气体及颗粒物起重要作用,氧化剂是降水酸化的控制剂;③在典型农村地区,降水化学组成依赖于降水云的化学组成,即依赖于云化学,酸化过程中SO_2是控制剂;④该地区主要氧化剂是H_2O_2,高度越高,云水中H_2O_2含量越高;⑤该地区是硫酸型酸雨,硝酸含量有上升趋势,在考虑降水酸度时有机酸贡献不可忽视;⑥降水中很多元素来自颗粒物,颗粒物缓冲参数化并耦合到云下洗脱模型中,大大缩小了观测与数值模拟的降水酸度之差.     

废茶活性炭脱硫脱硝性能的应用研究

为探讨废茶活性炭对于SO2和NO脱除作用的制约因素,分别考察了材料孔径结构、石墨化程度及表面结构对其脱硫脱硝性能的影响,同时研究了其吸附机制及动力学过程.结果表明,较高的石墨化程度是影响材料脱硫性能的主要因素,微孔径较小且含氮碱性基团较高时有利于SO2的脱除;发达的中孔结构是制约NO脱除效率的关键因素,含氮碱性基团对NO的脱除具有一定的促进作用;烟气中SO2和NO共存时,材料的脱硫脱硝性能均有所降低,氧气和水蒸气的加入能够改善其脱硫脱硝效率;废茶活性炭在无水环境下对于SO2和NO的吸附作用均以物理吸附为主,水蒸气的存在促进了材料对SO2的化学吸附;通过动力学模型的拟合发现,Bangham吸附模型能够很好地描述材料脱硫脱硝的动力学过程,其R2均高于0.989,材料对于SO2和NO的吸附速率常数均随氧气和水蒸气的加入而减小.     

In-cloud scavenging and deposition of sulfates and nitrates: Case studies and parameterization

Scavenging of sulfates and nitrates—two most common ions leading the cloudwater acidity—was investigated during field studies atop a site in Mt. Mitchell (35°44′05″N, 82°17′15″W) State Park where the highest peak (2038 m MSL) of the eastern U.S. is located. Experiments were conducted during the growing seasons (15 May–30 September) of 1986 and 1987 using an instrumented meteorological tower (16.5 m tall) and a passive cloudwater collector. A cloud episode that occurred on 12 October 1987, was also comprehensively investigated. Clouds were frequently observed in which the Fraser fir and red spruce stands stayed immersed 28% and 41% of the time during the 1986 and 1987 seasons, respectively. Rate of cloudwater deposition on the forest canopy was determined using an inferential cloud deposition model. It was found by analysing nine short duration (lasting 8 h or less) and 16 long duration cloud events that the ionic concentration (SO₄²⁻ and NO₃⁻) is inversely proportional to the rate (I_c) of cloudwater deposition (in mm h⁻¹) and can be expressed by the following relationship: [SO₄²⁻] = aI_c^−b or [NO₃⁻] = aI_c^−b. Theoretical arguments leading to these relationships are presented. The b values for predicting NO₃²⁻ concentration are found in the range of 0.14–1.24 (mean = 0.48) for short duration and 0.062–0.63 (mean = 0.27) for long duration cloud events, respectively. The corresponding b values for predicting NO₃⁻ concentrations are 0.19–1.16 (mean = 0.49) and 0.072–0.59 (mean = 0.27), respectively. When the b parameter was between 0.2 and 0.6, the correlation coefficients between measured and predicted ionic concentrations were found to exceed 0.7. The parameter a is shown to represent the maximum ionic flux for a given cloud event. The ratio of the a parameter for SO₄²⁻ to NO₃⁻ varied between 1.75 and 6.95, indicating that the SO₄²⁻ contributes to the total ionic concentration substantially more than the NO₃⁻ leading to the conclusion that the cloudwater acidity is primarily due to the presence of sulfuric acid which has been demonstrated to cause foliar injury and growth retardation in red spruce trees. The above parameterization is similar to the one that is frequently used to relate ionic concentration in precipitation to the rainfall rate. In order to understand physico-chemical processes leading to the proposed parameterization schemes, meteorological and chemical variables are comprehensively analysed for one short duration and two long duration cloud events. The concentrations of principal ions (SO₄²⁻, NO₃⁻, H⁺ and NH₄⁺) during the short duration cloud events were found to be much higher than those during the long duration ones, especially at colder temperatures. Such short cloud events have a potential of causing foliar narcosis in red spruce stands because of unusually acidic cloudwater to which these stands stay exposed intermittently during each growing season.     

Numerical evaluation of the effectiveness of NO2 and N2O5 generation during the NO ozonation process

Wet scrubbing combined with ozone oxidation has become a promising technology for simultaneous removal of SO₂ and NO_x in exhaust gas. In this paper, a new 20-species, 76-step detailed kinetic mechanism was proposed between O₃ and NO_x. The concentration of N₂O₅ was measured using an in-situ IR spectrometer. The numerical evaluation results kept good pace with both the public experiment results and our experiment results. Key reaction parameters for the generation of NO₂ and N₂O₅ during the NO ozonation process were investigated by a numerical simulation method. The effect of temperature on producing NO₂ was found to be negligible. To produce NO₂, the optimal residence time was 1.25 sec and the molar ratio of O₃/NO about 1. For the generation of N₂O₅, the residence time should be about 8 sec while the temperature of the exhaust gas should be strictly controlled and the molar ratio of O₃/NO about 1.75. This study provided detailed investigations on the reaction parameters of ozonation of NO_x by a numerical simulation method, and the results obtained should be helpful for the design and optimization of ozone oxidation combined with the wet flue gas desulfurization methods (WFGD) method for the removal of NO_x.