In-cloud scavenging of gases and aerosols at a mountain site in Central Switzerland

An in-cloud scavenging case study of the major ions (NH₄ ⁺, SO₄ ^2- and NO₃ ^-) determining the cloudwater composition at a mountain site (1620 m.a.s.l.) is presented. A comparison between in-cloud measurements of the cloudwater composition, liquid water content, gas concentrations and aerosol concentrations and pre-cloud gas and aerosol concentrations yields the following results. Cloudwater concentrations resulted from scavenging of about half of the available NH₃, aerosol NH₄ ⁺, aerosol NO₃ ^-, and aerosol SO₄ ^2-. Approximately a third of the SO₂ was scavenged by the cloudwater and oxidized to SO₄ ^2-. Cloud acidity during the first two hours of cloud interception (pH 3.24) was determined mostly by the scavenged gases (NH₃, SO₂, and HNO₃); aerosol contributions to the acidity were found to be small. Observations of gas and aerosol concentrations at three elevations prior to several winter precipitation events indicated that NH₃ concentrations are typically half (12–80 %) of the total (gas and aerosol) N (-III) concentrations. HNO₃ typically is present at much lower concentrations (1–55 %) than aerosol NO₃ ^-. Concentrations of SO₂ are a substantial component of total sulfur, with concentrations averaging 60 % (14–76 %) of the total S (IV and VI).     

采暖期和非采暖期西安大气颗粒物中水溶性组分的化学特征

为了探讨采暖期和非采暖期西安大气颗粒物水溶性组分的化学特征和来源,分别于2005年冬季(2005年12月-2006年2月)和2006年夏季(6～8月)采集西安大气PM2.5和TSP样品,分析其中Na+、NH4+、K+、Mg2+、Ca2+、F-、Cl-、Br-、NO-2、NO-3和SO2-4共11种水溶性离子的浓度,并对其季节特征和来源进行了研究.结果显示,采暖期西安大气PM2.5和TSP中11种水溶性离子的平均浓度分别为53.2μg·m-3和110.3μg·m-3,非采暖期分别为51.3 μg·m-3和89.3μg·m-3.SO2-4、NO-3和NH+4在PM2.5和TSP中均为最主要的离子组分,浓度之和在采暖期分别占到PM2.5和TSP总离子浓度的78%和76%,在非采暖期则占到88%和76%.PM2.5和TSP中,NH+4、SO2-4和NO-3三者之间都有很好的相关性,其在颗粒物中的主要结合形式为(NH4)2SO4、NH4 HSO4和NH4 NO3.硫的转化率(SOR)和氮的转化率(NOR)在非采暖期明显大于采暖期,揭示SO2-4和NO-3的形成机制为气相氧化,主要受温度的控制.阴阳离子平衡和pH值测定的结果表明西安市大气PM2.5稍偏酸性,TSP为碱性,无论是粗、细粒子采暖期比非采暖期更偏酸性.对比10年前的研究结果,显示西安市大气污染控制措施大大降低了采暖期气溶胶中二次组分的污染程度,但主要污染排放源已逐渐由燃煤型向机动车排放转化.     

上海市区和郊区黑碳气溶胶的观测对比

为了探讨上海市区和郊区黑碳气溶胶质量浓度、分布以及来源和输送等特征,利用上海浦东 (市区) 和东滩 (郊区河口湿地)2007年12月—2008年11月的黑碳气溶胶小时平均质量浓度数据,对比分析了两地黑碳气溶胶浓度在不同时间尺度上的变化特征以及气象要素对黑碳质量浓度的影响。结果表明:观测期间浦东和东滩两地黑碳气溶胶小时质量浓度平均值分别为3.8 μg·m-3,1.7 μg·m-3。两地黑碳气溶胶浓度具有类似的季节变化特征,均为冬季较高、夏季较低;同时浦东黑碳气溶胶浓度日变化呈现出明显的双峰结构,并具有显著的周末效应,体现了局地人为源排放的影响。受源排放影响为主的市区与受输送影响为主的郊区,黑碳气溶胶浓度在不同风向上与风速的关系表现出不同特征。     

A Long Term Study on Chemical Composition of Rainwater at Dayalbagh, a Suburban Site of Semiarid Region

Rainwater samples were collected for the monsoon period of 1988 and 1991–1996 at Dayalbagh (Agra), a suburban site situated in semiaridregion. The mean pH was 7.01 ±1.03 well above 5.6, which is the reference pH. Concentration of Ca²⁺ was observed to be highest followed by Mg²⁺, NH₄ ⁺,SO₄ ^2–, Cl^–,NO₃ ^–, Na⁺, F^– and K⁺. The ratios of SO₄ ^2– + NO₃ ^– andCa²⁺ + Mg²⁺ (TA/TC) have been considered as indicatorfor acidity. In the Agra region ratio of TA/TC is quite below 1.0 indicating alkaline nature of rainwater. The lowest value of 0.24 was observed in 1991 likely due to the lowest rain depth of the decade. The highest value of 0.54 was observed in 1996, a year with a large rain depth and increase in line (vehicular traffic) and area sources (population growth). Good correlation between Ca²⁺ and NO₃ ^–,Ca²⁺ and SO₄ ^2– andSO₄ ^2– and NO₃ ^–,indicates that wind carried dust and soil play a significant role in neutralization of precipitation acidity.     

Chemistry of Precipitation Events and Inter-Relationship with Ambient Aerosols over a Semi-Arid Region in Western India

The precipitation events (n = 91), collected for 3 years (2000–2002) during the period of SW-monsoon (Jun–Aug) from an urban site (Ahmedabad, 23.0°N, 72.6°E) of a semi-arid region in western India, are found to exhibit characteristic differences in terms of their solute contents. The low solute (<700 μeq L⁻¹) events are either marked by heavy precipitation amount or successive events collected during an extended rain spell; whereas light precipitation events occurring after antecedent dry period are characterized by high solutes (>700 μeq L⁻¹). The ionic composition of low solute events show large variability due to varying contribution of anthropogenic species (: 1%–74%; : 1%–25%; and : 8%–68%) to the respective ion balance. In high solute events, ionic abundances are dominated by mineral dust (Ca²⁺ and ) and sea-salts (Na⁺ and Cl⁻). These differences are also reflected in the pH of low solute events (range: 5.2–7.4, VWM: 6.4) and high solute events (range: 6.6–8.2, VWM: 7.3). The comparison of Ca²⁺/Na⁺ and nss- ratios (on equivalent basis) in rain and aerosols suggests that the ionic composition of high solute events is influenced by below-cloud scavenging; whereas evidence for in-cloud scavenging is significantly reflected in low solute events. The annual wet-deposition fluxes of and are 330 and 480 mg m⁻² y⁻¹, respectively, in contrast to their corresponding dry-deposition fluxes (14 and 160 mg m⁻² y⁻¹); whereas wet and dry removal of Ca²⁺, Mg²⁺ and are comparable.     

The influence of light intensity,SO2, NOx and C3H6 on sulfate aerosol formation

The photochemical oxidation of SO₂ in the presence of NO and C₃H₆ was studied in a 18.2 liter pyrex reactor. When light intensity, irradiation time and SO₂ concentration were constant, SO₄ ^2- concentration, derived from the total volume of aerosol produced, peaked when [C₃H₆]/[NO] was approximately 6.0. Another increase im SO₄ ^2- formation was reached at very high ratios (>50). The experimental observations are consistent with the two SO₂ oxidation mechanisms. At low [C₃H₆]/[NO] ratios, the processes proceed via the HO–SO₂ reaction, while at high ratios the O₃–C₃H₆ adduct is assumed to oxidize SO₂ to produce SO₄ ^2- aerosols.     

Modified HNO3 seasonality in volcanic layers of a polar ice core: Snow-pack effect or photochemical perturbation?

Using the chemical composition of snow and ice of a central Greenland ice core, we have investigated changes in atmospheric HNO₃ chemistry following the large volcanic eruptions of Laki (1783), Tambora (1815) and Katmai (1912). The concentration of several cations and anions, including SO ₄ ^2– and NO ₃ ^– , were measured using ion chromatography. We found that following those eruptions, the ratio of the concentration of NO ₃ ^– deposited during winter to that deposited during summer was significantly higher than during nonvolcanic periods. Although we cannot rule out that this pattern originates from snow pack effects, we propose that increased concentrations of volcanic H₂SO₄ particles in the stratosphere may have favored condensation and removal of HNO₃ from the stratosphere during Arctic winter. In addition, this pattern might have been enhanced by slower formation of HNO₃ during summer, caused by direct consumption of OH through oxidation of volcanic SO₂.     

A Case Study of the Impacts of Dust Aerosols on Surface Atmospheric Variables and Energy Budgets in a Semi-Arid Region of China

The authors present a case study investigating the impacts of dust aerosols on surface atmospheric variables and energy budgets in a semi-arid region of China. Enhanced observational meteorological data, radiative fluxes, near-surface heat fluxes, and concentrations of dust aerosols were collected from Tongyu station, one of the reference sites of the International Coordinated Energy and Water Cycle Observations Project (CEOP), during a typical dust storm event in June 2006. A comprehensive analysis of these data show that in this semi-arid area, higher wind velocities and a continuously reduced air pressure were identified during the dust storm period. Dust storm events are usually associated with low relative humidity weather conditions, which result in low latent heat flux values. Dust aerosols suspended in the air decrease the net radiation, mainly by reducing the direct solar radiation reaching the land surface. This reduction in net radiation results in a decrease in soil temperatures at a depth of 2 cm. The combination of increased air temperature and decreased soil temperature strengthens the energy exchange of the atmosphere-earth system, increasing the surface sensible heat flux. After the dust storm event, the atmosphere was dominated by higher pressures and was relatively wet and cold. Net radiation and latent heat flux show an evident increase, while the surface sensible heat flux shows a clear decrease.     

The solubility of SO2 and the dissociation of H2SO3 in NaCl solutions

The pK ₁ ^* and pK ₂ ^* of H₂SO₃ have been determined in NaCl solutions as a function of ionic strength (0.1 to 6 m) and temperature (5 and 25 °C). The extrapolated values in water were found to be in good agreement with literature data. The experimental results have been used to determine the Pitzer interaction parameters for SO₂, HSO ₃ ^- and SO ₃ ^- in NaCl solutions. The resultant parameters for NaHSO₃ and Na₂SO₃ were found to be in reasonable agreement with the values for NaHSO₄ and Na₂SO₄. It, thus, seems reasonable to assume that the interactions of Mg²⁺ and Ca²⁺ with HSO ₃ ^- and SO ₃ ^- can be estimated from the values with HSO ₄ ^- and SO ₄ ^- until experimental values are available. Measurements of pK ₁ ^* and pK ₂ ^* in artificial seawater were found to be in good agreement with the calculated values using the derived Pitzer parameters. It is, thus, possible to make reasonable estimates of the activity coefficients of HSO ₃ ^- and SO ₃ ^- ions and pK ₁ ^* and pK ₂ ^* for the ionization of H₂SO₃ in marine aerosols.     

临安冬夏季SO2、NO2和O3体积分数特征及与气象条件的关系

对临安大气本底站2003-2004年冬、夏季二氧化氮(NO2)、二氧化硫(SO2)、臭氧(O3)进行了分析.结果表明:冬季NO2和SO2平均体积分数分别为19.48×10-9和35.74 x10-9,而夏季的平均体积分数分别为4.81×10-9和8.12×10-9,冬季高于夏季;O3在夏季的平均体积分数为33.55×10-9,略高于冬季的25.44×10-9;夜间NO2和SO2体积分数比白天高,并且NO2呈明显的单峰单谷型分布,O3也呈单峰型但峰值出现在白天.NO2、SO2体积分数存在着明显的“假日效应”,假日比非假日低,周五高于假日和非假日;但O3体积分数没有明显的假日效应.降水对SO2有明显的清除作用,但对NO2的清除作用不明显.与风向对比发现,夏季高体积分数的NO2、SO2都受到NW、WNW风的影响,冬季则分别受NE和SW、SSW风的影响;而O3受风向的影响较复杂,与局地光化学反应有关.     

城市大气气溶胶的物理化学特性及其对人体健康的影响

根据在北京、重庆、上海等城市大气气溶胶的观测结果和气溶胶中有机化学成分的有关资料,分析城市地区大气气溶胶的浓度、尺度谱分布、日变化规律及其化学成分的谱分布特征,并与干净地区的结果作比较,进而探讨了大气气溶胶对人体健康的影响。     

Seasonal variations of atmospheric sulfur dioxide and dimethylsulfide concentrations at Amsterdam Island in the southern Indian Ocean

Daily measurements of atmospheric sulfur dioxide (SO₂) concentrations were performed from March 1989 to January 1991 at Amsterdam Island (37°50 S–77°30 E), a remote site located in the southern Indian Ocean. Long-range transport of continental air masses was studied using Radon (²²²Rn) as continental tracer. Average monthly SO₂ concentrations range from less than 0.2 to 3.9 nmol m^-3 (annual average = 0.7 nmol m^-3) and present a seasonal cycle with a minimum in winter and a maximum in summer, similar to that described for atmospheric DMS concentrations measured during the same period. Clear diel correlation between atmospheric DMS and SO₂ concentrations is also observed during summer. A photochemical box model using measured atmospheric DMS concentrations as input data reproduces the seasonal variations in the measured atmospheric SO₂ concentrations within ±30%. Comparing between computed and measured SO₂ concentrations allowed us to estimate a yield of SO₂ from DMS oxidation of about 70%.     

Mass transfer at the air/water interface: Mass accommodation coefficients of SO2, HNO3, NO2 and NH3

We present here experimental determinations of mass accommodation coefficients using a low pressure tube reactor in which monodispersed droplets, generated by a vibrating orifice, are brought into contact with known amounts of trace gases. The uptake of the gases and the accommodation coefficient are determined by chemical analysis of the aqueous phase.We report in this article measurements of _exp=(6.0±0.8)×10^–2 at 298 K and with a total pressure of 38 Torr for SO₂, (5.0±1.0)×10^–2 at 297 K and total pressure of 52 Torr for HNO₃, (1.5±0.6)×10^–3 at 298 K and total pressure of 50 Torr for NO₂, (2.4±1.0)×10^–2 at 290 K and total pressure of 70 Torr for NH₃.These values are corrected for mass transport limitations in the gas phase leading to =(1.3±0.1)×10^–1 (298 K) for SO₂, (1.1±0.1)×10^–1 (298 K) for HNO₃, (9.7±0.9)×10^–2 (290 K) for NH₃, (1.5±0.8)×10^–3 (298 K) for NO₂ but this last value should not be considered as the true value of for NO₂ because of possible chemical interferences.Results are discussed in terms of experimental conditions which determine the presence of limitations on the mass transport rates of gaseous species into an aqueous phase, which permits the correction of the experimental values.     

Chemical Composition of Summertime PM2.5 and Its Relationship to Aerosol Optical Properties in Guangzhou, China

Urban aerosols have a large effect on the deterioration of air quality and the degradation of atmospheric visibility.Characterization of the chemical composition of PM 2.5 and in situ measurements of the optical properties of aerosols were conducted in July 2008 at an urban site in Guangzhou,Southern China.The mean PM 2.5 concentration for the entire period was 53.7±23.2 μg m 3.The mean PM 2.5 concentration (82.7±25.4 μg m 3) on hazy days was roughly two times higher than that on clear days (38.8±8.7 μg m 3).The total water-soluble ion species and the total average carbon accounted for 47.9%±4.3% and 35.2%±4.5%,respectively,of the major components of PM 2.5.The increase of secondary and carbonaceous aerosols,in particular ammonium sulfate,played an important role in the formation of haze pollution.The mean absorption and scattering coefficients and the single scattering albedo over the whole period were 53±20 M m 1,226±111 M m 1,and 0.80±0.04,respectively.PM 2.5 had a high linear correlation with the aerosol extinction coefficient,elemental carbon (EC) was correlated with aerosol absorption,and organic carbon (OC) and SO 4 2 were tightly linked to aerosol scattering.     

南京市城市不同功能区PM10和PM2.1质量浓度的季节变化特征

使用Anderson-Ⅱ型9级撞击采样器测量了南京市鼓楼商业区、江北工业区、钟山风景区和宁六高速公路交通源春、夏、秋三季的大气气溶胶质量浓度。分析结果表明:南京市PM_2.1和PM₁₀的质量浓度存在明显的季节变化,秋季>春季>夏季;ρ_PM10春季为167.47 μg/m³,夏季为 85.99 μg/m³,秋季为238.99 μg/m³;ρ_PM2.1春季为59.66 μg/m³,夏季为42.80 μg/m³,秋季为100.15 μg/m³。不同季节中ρ_PM10和ρ_PM2.1均存在较好的相关性,夏季相关性最好,相关系数为0.952;秋季次之,相关系数为0.783;春季相对较差,相关系数为0.613。城市不同功能区之间ρ_PM2.1和ρ_PM10的质量浓度值差异很大,交通源>工业区>商业区>风景区。城市不同功能区的质量浓度谱分布基本一致,均为双峰型分布,峰值分别位于0.43~0.65 μm/m³和9.0~10.0 μm/m³。南京市春、夏、秋三个季节大气粒子质量浓度谱为双峰分布,粒子主要集中在0.43~3.3 μm/m³的粒径段。江北工业区ρ_PM10和ρ_PM2.1质量浓度的相关系数为0.814,略高于鼓楼商业区的0.797。     

不同降水强度对PM2.5的清除作用及影响因素

云和降水过程是大气污染物的重要清除途径,但由于降水过程和大气污染颗粒物本身的复杂性,目前降水过程对大气污染物的清除机制及影响因素有待深入研究。该文利用2014年3月—2016年7月在北京地区连续观测的PM_2.5和降水数据,研究了不同降水强度对PM_2.5的清除率,以及雨滴谱、风速和降水持续时间对PM_2.5清除率的影响。研究表明:降水强度越大,对PM_2.5清除效率越高。小雨、中雨和大雨对PM_2.5清除率平均值分别为5.1%,38.5%和50.6%。小雨不但对PM_2.5的清除率最低,而且对PM_2.5的清除效果也存在很大差异,约50%的小雨个例中PM_2.5质量浓度出现减小情况,而另外50%的小雨个例中,PM_2.5质量浓度出现增加情况。在持续时间长或地面风速增大的情况下,小雨也表现出较高的清除率。在中雨和大雨情况下,PM_2.5质量浓度均出现明显减小情况。但降水持续时间和风速对中雨和大雨的清除率影响较小,这是由于中雨和大雨一般在较短时间内即可清除大部分PM_2.5,因此,对降水的持续时间和风速大小不敏感。     

Growth Rates of Fine Aerosol Particles at a Site near Beijing in June 2013

Growth of fine aerosol particles is investigated during the Aerosol–CCN–Cloud Closure Experiment campaign in June2013 at an urban site near Beijing. Analyses show a high frequency(~ 50%) of fine aerosol particle growth events, and show that the growth rates range from 2.1 to 6.5 nm h~(-1) with a mean value of ~ 5.1 nm h~(-1). A review of previous studies indicates that at least four mechanisms can affect the growth of fine aerosol particles: vapor condensation, intramodal coagulation,extramodal coagulation, and multi-phase chemical reaction. At the initial stage of fine aerosol particle growth, condensational growth usually plays a major role and coagulation efficiency generally increases with particle sizes. An overview of previous studies shows higher growth rates over megacity, urban and boreal forest regions than over rural and oceanic regions. This is most likely due to the higher condensational vapor, which can cause strong condensational growth of fine aerosol particles.Associated with these multiple factors of influence, there are large uncertainties for the aerosol particle growth rates, even at the same location.     

南京市城市不同功能区PM10和PM2.1质量浓度的季节变化特征

使用Anderson-Ⅱ型9级撞击采样器测量了南京市鼓楼商业区、江北工业区、钟山风景区和宁六高速公路交通源春、夏、秋三季的大气气溶胶质量浓度。分析结果表明:南京市PM_2.1和PM₁₀的质量浓度存在明显的季节变化,秋季>春季>夏季;ρ_PM10春季为167.47 μg/m³,夏季为 85.99 μg/m³,秋季为238.99 μg/m³;ρ_PM2.1春季为59.66 μg/m³,夏季为42.80 μg/m³,秋季为100.15 μg/m³。不同季节中ρ_PM10和ρ_PM2.1均存在较好的相关性,夏季相关性最好,相关系数为0.952;秋季次之,相关系数为0.783;春季相对较差,相关系数为0.613。城市不同功能区之间ρ_PM2.1和ρ_PM10的质量浓度值差异很大,交通源>工业区>商业区>风景区。城市不同功能区的质量浓度谱分布基本一致,均为双峰型分布,峰值分别位于0.43~0.65 μm/m³和9.0~10.0 μm/m³。南京市春、夏、秋三个季节大气粒子质量浓度谱为双峰分布,粒子主要集中在0.43~3.3 μm/m³的粒径段。江北工业区ρ_PM10和ρ_PM2.1质量浓度的相关系数为0.814,略高于鼓楼商业区的0.797。     

Gas-Particle Partitioning of Nitric Acid Modulated by Alkaline Aerosol

The role of alkaline mineral aerosol in controlling HNO₃ partitioning between gas and aerosol phases is explored using a comprehensive, process oriented three-dimensional model. Simulation results for March 1994, a period from the PEM West B experiment, are presented. It is found that in the dust impacted regions of the boundary layer and free troposphere, more than 50% of HNO₃ ispartitioned onto dust particles; while 1050% of HNO₃ in the boundarylayer and 10 30% of HNO₃ in the free troposphere is partitionedonto sea-salt particles. This higher capacity of mineral dust to uptake HNO₃ is due to the fact that carbonate in the dust particles is more volatile (thus easily replaced by nitrate) than chloride in the sea-salt particles. When this process of nitric acid partitioning onto alkaline particles is included in the analysis, model predicted HNO₃-to-NO_x ratios are much closer to observed valuesthat typically range between 1 and 9.