A photochemical box model for urban air quality study

The photochemical box model (PBM) developed in the present study is based on the principle of mass conservation. It has a horizontal domain of the size of a typical city and a vertical dimension defined by the mixed-layer height. The concentration of any pollutant is determined by horizontal advection, vertical entrainment, source emissions and chemical reactions. A one-dimensional high resolution boundary layer model by Blackadar (Preprints, Third Symp. on Atmospheric Turbulence, Diffusion, and Air Quality, Raleigh, Am. Met. Soc., pp. 443–447, 1976; Advances in Environmental Sciences and Engineering, Vol. 1, No. 1 (edited by Pfafflin J. and Ziegler E.), pp. 50–85. Gordon and Breach, New York, 1979) has been incorporated in the PBM and further developed to consider the effect of urban heat islands in the simulation of mixed layer height. The predicted mixed-layer heights compare very well with observations. The gas phase chemical kinetic mechanism used in the Regional Acid Deposition Model II (RADM2) and that of an earlier version of PBM have been used to calculate the contributions of chemical reactions to the changes of pollutant concentrations. Detailed analysis and comparisons of the two chemical mechanisms have been made. The simulated pollutant concentrations using both chemical mechanisms are in very good agreement with available observations for CO, NO, NO₂ and O₃. A radiative transfer model developed by Madronich (J. geophys. Res.92, 9740–9752, 1987) has been incorporated in the PBM for the calculation of actinic flux and photolytic rate constants. Height-averaged and radiation-corrected photolytic rate constants are used for the photochemical reactions. Budget analyses conducted for CO, NO, NO₂ and O₃ have enhanced our understanding of the relative contributions of horizontal advection, vertical entrainment, source emissions and chemical reactions to the overall rate of change of their concentrations. Model predictions are not sensitive to the large number of peroxy radical-peroxy radical reactions in the RADM2 chemical mechanism under urban conditions.     

An estimation of the average annual transports of SO2 from the CSFR and the former G.D.R. to north-east Bavaria

A mesoscale flow model is used to evaluate a climatology of flow and SO₂ concentration for north-east Bavaria. The computed average SO₂ concentrations at ground level are compared with observations and good agreement is found. This allows estimation of the average annual transport of SO₂ from Czechoslowakia and the former G.D.R. to north-eastern Bavaria on the basis of these climatologies. An annual SO₂ transport of 188 kt from CSFR and 278 kt from the former G.D.R. to north-east Bavaria is found.     

多元观测资料融合应用的灰霾天气关键成因研究

利用临安作为区域大气本底站的优势和杭州大气复合污染综合观测设施,再融合DMSP/OLS夜间灯光数据及气象观测数据,从不同层面研究了灰霾天气形成的主导因素.通过浙江省灰霾日数空间分布与同时期Defense Meteorological Satellite System (DMSP)/Operational Linescan System (OLS)卫星遥感得到的夜间灯光分布对比以及1960-2009年间杭州和浙江省年平均灰疆日数演变过程,从空间和年代际变化两个角度论证了当前不科学的社会发展是造成灰霾天气日益严重的根本原因.通过杭州和临安本底站实际观测对比发现,对灰霾天气形成起主要作用的是细粒子,关键排放因子不是尘粒等气溶胶,而是黑碳、NO2、SO2等.脱硫减排可以使霾污染有所减缓,但由汽车尾气等排放的含氮前体物对霾污染的贡献却越显突出.气象条件是灰霾天气形成的外部控制因素.在各种天气形势中,由于高压控制下下沉气流明显、大气相对稳定,出现灰霾天气的概率最高,达64.5％.除天气形势、大气稳定度外,风速、气温、湿度、气压、降水、变温等地面气象因子及前1日PM10浓度对污染物浓度皆有一定影响,其中降水、湿度、风速与污染物浓度之间的相关性最显著,是灰霾天气形成的关键气象因子.     

Aspects of wet,acidifying deposition in Arnhem: Source regions,correlations and trends (1984–1991)

A time series of wet deposition in Arnhem, the Netherlands, was analysed for the period 1984–1991. Precipitation was collected with four samplers on a daily basis. A comparative study by the Dutch National Precipitation Network showed significant biases for the observations of the National Network station due to longer exposure to dry deposition. Simultaneous operation of wet-only and bulk collectors demonstrated a concentration bias of about 10% for daily bulk sampling.Using a cluster analysis of backward trajectories, clear distinctions could be made between precipitation from continental and maritime origin. Event-to-event variations in deposition seemed to be determined largely by meteorological influences. As major anthropogenic source regions, the U.K., France, Belgium and the Netherlands itself were identified. The contribution of Dutch sources to wet acid deposition in Arnhem was estimated at 30–40%.Trends and seasonal variations were analysed with an advanced time-series model based on Kalman filtering. Similar seasonal variations were found for SO₄²⁻ and NH₄⁺. Also, seasonal variations in the concentrations of H⁺ and NO₃⁻ corresponded. Significant long-term changes in deposition and concentration were found for SO₄²⁻ (about −3% yr⁻¹) and H⁺ (about −9% yr⁻¹) only. The analysed trends were decreasing, but decreases were larger in the years 1984–1986 than in the following years. The relative decrease in the wet deposition of SO₄²⁻ was substantially smaller than decrease in dry-deposited SO₂ and SO₄²⁻.     

Transported acid aerosols measured in southern Ontario

During the period 29 June 1986–9 August 1986, a field health study assessing the acute health effects of air pollutants on children was conducted at a summer girls' camp on the northern shore of Lake Erie in SW Ontario. Continuous air pollution measurements of SO₂, O₃, NO_x, particulate sulfates, light scattering, and meteorological measurements including temperature, dew point, and wind speed and direction were made. Twelve-hour integrated samples of size fractioned particles were also obtained using dichotomous samplers and Harvard impactors equipped with an ammonia denuder for subsequent hydrogen ion determination. Particulate samples were analyzed for trace elements by X-ray fluorescence and Neutron Activation, and for organic and elemental carbon by a thermal/optical technique. The measured aerosol was periodically very acidic with observed 12-h averaged H⁺ concentrations in the range < 10–560 nmoles m⁻³. The aerosol H⁺ appeared to represent the net strong acidity after H₂SO₄ reaction with NH₃(g). Average daytime concentrations were higher than night-time for aerosol H⁺, sulfate, fine mass and ozone. Prolonged episodes of atmospheric acidity, sulfate, and ozone were associated with air masses arriving at the measurement site from the west and from the southwest over Lake Erie. Sulfate concentrations measured at the lakeshore camp were more than twice those measured at inland sites during extreme pollution episodes. The concentration gradient observed with onshore flow was potentially due to enhanced deposition near the lakeshore caused by discontinuities in the meteorological fields in this region.     

2013年1月华北地区重霾污染过程SO2和NOx的CMAQ源同化模拟研究

以2006年中国地区的INTEX-B排放清单为基础,采用CMAQ模式污染源同化方法,反演更新了2013年1月重霾污染过程华北地区的SO₂和NO_x排放源;应用WRF-CMAQ模式以及2006年INTEX-B初始排放源和2013年1月改进的排放源,分别模拟了1月9-15日和28-31日两次持续重霾污染过程的SO₂和NO₂浓度,并与华北地区47个环境监测站点实测值进行对比,重点分析了基于初始源和同化反演源的模拟效果及其改进原因;本文亦采用2012年清华大学编制的东亚地区MEIC排放清单评估了SO₂和NO_x同化反演源的合理性.分析结果表明:①CMAQ模式污染源同化方法可适用于重霾污染过程,即采用同化反演源模拟的SO₂、NO₂浓度时空变化特征与实测值较一致,而且可反映SO₂、NO_x排放源强的动态变化特征;②基于同化反演源的SO₂、NO₂浓度模拟效果明显优于2006年INTEX-B排放源,其时间变化趋势与实测值较一致,而且可模拟重霾污染过程SO₂、NO₂浓度的峰值;③采用反演源模拟的SO₂、NO₂浓度空间区分布特征与实测值较一致,而且可较好反映重污染区的极值分布特征;④经污染源同化改进后SO₂、NO₂模拟浓度与实测值的相关系数有所提高,误差明显减小;SO₂的改进效果略优于NO₂,这与污染源对两种污染物浓度的影响差异有关;⑤初始源中SO₂、NO_x排放源的空间分布和强度与2012年清华大学编制的排放源强差异较大,而同化反演源的空间分布和强度均接近于上述2012年排放源,较好反映出重点地区的高污染源分布特征.本文研究结果将为改进重霾污染过程的空气质量预报、减小自下而上建立的排放源清单不确定性、评估SO₂、NO_x等排放源的影响效应以及不同气象条件下区域排放源的动态调控等提供新技术途径和研究思路.     

基于BP神经网络的大气污染物浓度预测

利用BP神经网络结合变量筛选的方法建立了SO_2、NO_2、O3、CO、PM_(10)、PM_(2.5)等6种污染物的浓度预测模型,并选取2014-01-01至2015-11-28时段,昆明市区5个环境监测点以上6种污染物浓度的监测数据建立了昆明市污染物日均浓度预测模型.采用平均影响值(Mean Impact Value,MIV)的方法筛选出分别对6种污染物日均浓度值有主要影响的变量,作为BP神经网络的输入变量,利用建立的预测模型分别对6种污染物的日均浓度进行预测.结果表明,在关上监测点利用浓度预测模型对SO_2、NO_2、O3、CO、PM_(10)、PM_(2.5)等6种污染物浓度进行预测,污染物浓度预测值和实测值趋势吻合度较高.变量筛选后SO_2、PM_(2.5)预测效果比变量筛选前的预测效果好.O3的均方根误差和PM_(10)的标准化平均偏差,变量筛选前的预测效果比变量筛选后的预测效果好.变量筛选前的NO_2和CO的预测结果比变量筛选后的预测效果好.其他4个环境监测点的污染物浓度预测结果与关上监测点的结果相似.     

基于船舶实时排放和烟羽在线监测的燃油硫含量识别方法研究

船用燃油超标识别方法的建立和技术发展是进行船舶排放控制区（Domestic Emission Control Areas,DECA）政策执行的重要保障.本研究建立了基于船舶自动识别系统（Automatic Identification System,AIS）数据的船舶排放实时计算模型和岸基环境观测相结合的技术方法,选取上海吴淞口航道水域开展实地外场观测实验,实现了对观测船只排放烟羽中SO₂和NO₂浓度的在线观测和对燃油硫含量（Fuel Sulfur Content,FSC）进行同步识别和反算.观测期间,通过差分吸收光谱（Differential Optical Absorption Spectroscopy,DOAS）技术共捕捉到1505艘次船舶的烟羽.经过观测截面的船舶总吨位为30~14308 t,船舶排放烟羽浓度峰值的平均持续时间为3~10 min.受船舶烟羽影响期间,SO₂和NO₂的浓度增量分别在0.03~35.51 ppb和0.02~39.26 ppb之间,实时排放模型估算出SO₂和NO₂的排放强度分别为1.32~28.06 g·min^-1和2.89~123.80 g·min^-1.结合在线观测和实时排放模型基于硫氮比对船用燃油硫含量进行反算识别,并与实测燃油硫含量数据样本进行对比验证,结果表明,实际燃油硫含量在0.05%以上时,反算硫含量数值误差在10%以内.本研究可为船舶燃油超标识别提供新的技术思路,并为船舶排放控制区政策落实提供科学基础.     

Modeling of SO2, Pb and Cd atmospheric deposition over a one-year period

Atmospheric deposition of SO₂, and fine particles of Pb and Cd are calculated over a one-year period in a 66 km² airshed with a segment-puff model. Emission variations, hourly mixing heights and meteorological values are considered to compute monthly averages of concentrations and deposition. Dry deposition is calculated by means of deposition velocities which are season- and land use-dependent. Wet deposition is determined using a washout coefficient. To assess the simulation performance, calculated SO₂ results from the combination between the deposition velocity, the windspeed and direction and the location and type of sources. As annual averages, results for dry plus wet deposition are computed to be 0.84 mg m⁻²d⁻¹ for sulfur, 4.15 μgm⁻²d⁻¹ for lead and 0.0013 μgm⁻²d⁻¹ for cadmium. A variation factor is derived from a sensitivity analysis. This factor amounts to 2.3−2.8 for the concentrations and 2.6−3.1 for the deposition, depending on the pollutant.     

A land use regression model incorporating data on industrial point source pollution

Advancing the understanding of the spatial aspects of air pollution in the city regional environment is an area where improved methods can be of great benefit to exposure assessment and policy support. We created land use regression (LUR) models for SO₂, NO₂ and PM₁₀ for Tianjin, China. Traffic volumes, road networks, land use data, population density, meteorological conditions, physical conditions and satellite-derived greenness, brightness and wetness were used for predicting SO₂, NO₂ and PM₁₀ concentrations. We incorporated data on industrial point sources to improve LUR model performance. In order to consider the impact of different sources, we calculated the PSIndex, LSIndex and area of different land use types (agricultural land, industrial land, commercial land, residential land, green space and water area) within different buffer radii (1 to 20 km). This method makes up for the lack of consideration of source impact based on the LUR model. Remote sensing-derived variables were significantly correlated with gaseous pollutant concentrations such as SO₂ and NO₂. R² values of the multiple linear regression equations for SO₂, NO₂ and PM₁₀ were 0.78, 0.89 and 0.84, respectively, and the RMSE values were 0.32, 0.18 and 0.21, respectively. Model predictions at validation monitoring sites went well with predictions generally within 15% of measured values. Compared to the relationship between dependent variables and simple variables (such as traffic variables or meteorological condition variables), the relationship between dependent variables and integrated variables was more consistent with a linear relationship. Such integration has a discernable influence on both the overall model prediction and health effects assessment on the spatial distribution of air pollution in the city region.     

The impact of Swedish SO2 policy instruments on SO2 emissions 1990–2012

Sulphur dioxide (SO₂) emissions cause acidification and human health problems which are, despite present policy instruments, projected to remain even after 2030 in Europe. Additional instruments are needed to solve the problems, and impact analysis of already used policy instruments would contribute to the development of new effective instruments. We present a study on how much of the decoupling of SO₂ emissions from economic growth 1990–2012 that was due to SO₂ policy instruments in general and to what extent it is possible to estimate the impact of individual instruments. Focus is on Sweden, a country with problems reaching its SO₂-related environmental policy targets and with detailed data available.We applied decomposition analysis combined with an analysis of the chronological development of emission factors and mandated emission limits. Our use of official emission inventory data and publicly available data on the development of SO₂ policy instruments increase the usefulness of our results to policy makers.The results indicate that at least 26–27% (corresponding to ∼35–36 ktonne annually) of the decoupling 1990–2012 was due to SO₂ policy instruments. 4–5% (∼6–7 ktonne) of the decoupling was caused by one environmental permit decision and stricter sulphur emission limit for marine oils. Most of the total impact of SO₂ policy instruments could not be causally connected to an individual instrument, because many events and developments overlap in time.The implications of the results are that: a) SO₂ policy instruments should still be important to reduce SO₂ emissions in many countries; b) a lower boundary total emission impact of SO₂ policy instruments can be estimated, but with current knowledge and data the impacts of individual instruments are rarely possible to estimate. Research on how to increase the precision in total impact estimates of SO₂ policy instruments is needed to improve future impact analyses. More detailed emission inventory data would improve impact analysis of individual instruments.     

Products and mechanism of the reaction between NO3 and dimethylsulphide in air

The reaction between NO₃ and dimethylsulphide (DMS) in air has been studied in a 480 ℓ reaction chamber. Intermediates and end products were identified by FT-IR and ion chromatography.HNO₃, CH₂O, SO₂ and methanesulphonic acid were found to be the main products of the reaction, with methanesulphonic acid as the most abundant sulphur compound. Organic peroxynitrates and CH₃SNO₂ have been identified as intermediates from their characteristics spectral features. Based on the results obtained a mechanism for the reaction DMS+NO₃ is proposed, which has hydrogen abstraction as the first step. The formation of HNO₃ followed by removal of HNO₃ by deposition may represent an efficient night-time sink of NO_x in the marine troposphere.     

A case study of Asian dust storm particles: Chemical composition, reactivity to SO2 and hygroscopic properties

Mineral dust comprises a great fraction of the global aerosol loading, but remains the largest uncertainty in predictions of the future climate due to its complexity in composition and physico-chemical properties. In this work, a case study characterizing Asian dust storm particles was conducted by multiple analysis methods, including SEM-EDS, XPS, FT-IR, BET, TPD/mass and Knudsen cell/mass. The morphology, elemental fraction, source distribution, true uptake coefficient for SO₂, and hygroscopic behavior were studied. The major components of Asian dust storm particles are aluminosilicate, SiO₂ and CaCO₃, with organic compounds and inorganic nitrate coated on the surface. It has a low reactivity towards SO₂ with a true uptake coefficient, 5.767×10^-6, which limits the conversion of SO₂ to sulfate during dust storm periods. The low reactivity also means that the heterogeneous reactions of SO₂ in both dry and humid air conditions have little effect on the hygroscopic behavior of the dust particles.     

Sulfur dioxide reactions on ice surfaces: implications for dry deposition to snow

Controlled exposure of ice to a reactive gas, SO₂, demonstrated the importance of the chemical composition of the ice surface on the accumulation of acidity in snow. In a series of bench-scale continuous-flow column experiments run at four temperatures (−1, −8, −30 and −60°C), SO₂ was shown to dissolve and to react with other species in the ice-air interfacial region at temperatures approaching the melting point of ice. Experiments consisted of passing air containing SO₂ through glass columns packed with 100μm ice spheres of varying bulk composition (0–5μM H₂O₂, and 0–1 mM NaCl), and analysing SO₂ in the air and SO₄²⁻ in the ice. At all temperatures (−60 to −1°C), increased retention volumes were found for increasing ionic strength and oxidant concentration. At the coldest temperatures and with no NaCl, increased retention volumes for −60 vs −30°C are consistent with SO₂ uptake by physical adsorption. At warmer temperatures, −8 and −1°C, the observed tailing in the sorption curves indicated that other processes besides physical adsorption were occurring. The desorption curves showed a rapid decrease for the warmer temperatures, indicating the sorbed SO₂ is irreversibly oxidized to SO₄²⁻. Results indicate that aqueous-phase reactions can occur below −8°C (i.e. −30 and −60°C). Results for different salt concentrations show that increasing ionic strength facilitates SO₂ oxidation at colder temperatures, which is consistent with freezing point depression. One environmental implication is that snowpacks in areas with background SO₂, can accumulate acidity during the winter months. As acidity accumulates, the solubility of SO₂ will decrease causing a concomitant decrease in the air-to-surface flux of SO₂. Modeling dry deposition of gases to snow surfaces should incorporate the changing composition of the ice surface.     

A long-term (1975–1988) study of atmospheric SO42−: Regional contributions and concentration trends

A long-term study of aerosol SO₄²⁻ concentrations ([SO₄²⁻]) has been conducted at Mayville in the western and Whiteface Mountain in the northeastern New York State. From 1975 to 1988, 2382 daily aerosol samples were collected at Whiteface Mountain using high-volume samplers. Similarly, 1863 samples were collected at Mayville for the 1981–1988 period. Both sites are downwind of large SO₂ sources in the Midwest. Whiteface Mountain is located approximately 600 km to the northeast of Mayville. The [SO₄²⁻] at Mayville were approximately twice that of Whiteface Mountain. The highest concentrations at both locations were observed in summer and the lowest during winter. Photochemical reactions appear to be the primary reason for this behavior. Air trajectories (Hefter model) were used to relate the observed [SO₄²⁻] with the upwind SO₂ source regions. In addition, a method based on V/Se ratios was used to resolve SO₄²⁻ contributions between Midwestern sources and those in the East Coast. Approximately, two-thirds or more of the total SO₄²⁻ at the two sites was derived from the Midwestern emissions. At Whiteface Mountain the [SO₄²⁻] for summer months from 1975 to 1988 suggest a decrease of approximately 3% per year between 1978 and 1988. A similar decrease was also observed in SO₂ emissions.     

A non-local closure model for vertical mixing in the convective boundary layer

A simple non-local closure model for vertical mixing in Convective Boundary Layers (CBL) has been developed specifically for application in regional or mesoscale atmospheric chemistry models. The model, named the Asymmetrical Convective Model (ACM), is based on the concept that vertical transport within the CBL is inherently asymmetrical. Upward transport by buoyant plumes originating in the surface layer is simulated by mixing from the lowest model layer directly to all other layers in the CBL. Downward transport, however, proceeds only to the next layer in order to emulate gradual compensatory subsidence. The ACM is similar to the model developed by Blackadar (1978, 4th Symp. on Atmospheric Turbulence, Diffusion and Air Quality, pp. 443–447, Reno, Am. Meteorol. Soc.) but differs in its treatment of downward transport. The realism of the ACM is tested through comparisons to large-eddy simulations of several idealized test cases. These tests show that while the ACM shares the Blackadar model's ability to simulate rapid transport upward from the surface layer to all levels in the CBL, it is clearly superior in its treatment of material emitted from elevated sources either within or above the CBL. The ACM is also tested in the context of the Regional Acid Deposition Model (RADM) both to determine sensitivity to different CBL mixing schemes and to compare to vertically resolved aircraft measurements. These tests demonstrate quicker upward transport of ground-level emissions by the ACM as compared to the eddy diffusion scheme currently used in RADM. The ACM also affects ozone photochemistry in the boundary layer resulting in lower ozone concentrations in areas of high NO_x emissions.     

SO_2体积分数对ZL50活性炭吸附脱硫行为的影响和动力学分析

通过动态吸附烟气脱硫实验,考察了烟气中不同SO2体积分数对ZL50脱硫脱硝活性炭脱硫行为的影响,并进行了动力学分析.随着烟气中SO2体积分数增大,脱硫率和ZL50脱硫脱硝活性炭的活性度下降;SO2吸附量和吸附速率增大.模拟结果表明,Bangham模型模拟效果最优,SO2的催化氧化反应对化学吸附有重要影响;Lagergren准一级吸附速率常数随SO2进口体积分数的增加而增大,表明SO2的催化氧化反应在吸附前期可能为速控步骤.推导和定义了Lagergren模型和Bangham模型的初始吸附速率;推导了文献上的Ho模型和Elovich模型的初始速率式。定义的Bangham初始吸附速率与初始吸附速率实验值吻合最好;建立的Bangham吸附反应动力学模型能较好地描述SO2动态吸附速率.结果表明,SO2的初始反应速率分级数为1或接近1,而O2和水蒸气的初始速率分级数分别为0.15～0.20和0.45～0.50之间的常数.     

Calculation of visual range improvements from SO2 emission controls—I. Semi-empirical methodology

This paper, the first of a two-part series, presents a new semi-empirical methodology that allows estimation of the percentage improvements in annual average visual range that can be expected from a percentage reduction of SO₂ emissions. This methodology relies on an intuitive mathematical approach that combines four separate effects: (1) the transport of atmospheric sulfur; (2) the possible nonlinearity of the SO₂-to-SO²⁻₄ chemical transformation; (3) the fraction of sulfates in fine particulate matter, taking into account the role of the water adsorbed by the fine particles; and (4) the fraction of light extinction that is due to fine particles. By looking at these four effects, within the context of each of the various meteorological regimes that have distinct influences on visual air quality, the problem can be broken down into manageable components that model a portion of the source-receptor interaction. If the necessary arrays that specify these four terms, which are expressed in fractional form, can be quantified for each region and meteorological classification, then the methodology can estimate the average ‘efficiency’ of reductions in SO₂ emissions for producing improvements in long-term regional averages of visual range. Then, annual averages can be computed if the relative frequency of occurrence of each meteorological regime in each region is known. Moreover, the method estimates the uncertainty in the calculated percentage improvements in visual range, based on the uncertainties in input data. The second paper in this series will present an example of the application of this methodology to the eastern U.S., where the effect of SO₂ emissions on visibility has received significant attention.