A diffusion tube survey of NO2 levels in urban areas of the U.K.

A nationwide survey of ambient NO₂ concentrations has been carried out by Warren Spring Laboratory and AEA Technology, Harwell, in urban areas of the U.K. The survey utilised passive diffusion tube samplers, deployed at 363 existing smoke/SO₂ monitoring stations, and ran from July to December 1986.Although undertaken primarily to provide an independent check on the siting of monitoring stations to determine compliance with the European Community NO₂ Directive, the survey provides for the first time a nationwide picture of urban levels of this pollutant. London was found to experience the highest average NO₂ concentrations in the U.K., with these being highest close to busy roads. Concentrations were found to be only moderately higher in winter than in summer.Correlations between measurements of SO₂, smoke and NO₂ were examined. The closest correlation is observed between NO₂ and smoke, indicating traffic to be a dominant source of these pollutants. NO₂ data are also shown to correlate well with disaggregated NO_x emission data for the U.K.     

Dispersion modelling of nitrogen oxides in the United Kingdom

This paper describes the construction and application of an Eulerian-dispersion model for the calculation of NO₂ and NO_x concentrations in the U.K. Model results are compared with measurements from 44 U.K. sites. The sensitivity of the model results to chemical and dispersion parameterisations is assessed. The model is also used to verify the validity of ‘instantaneous mixing’ assumptions used in trajectory models. Finally, the distribution of ground-level NO_x concentrations from power stations, motor vehicles and other stationary sources is calculated across the U.K., including a preliminary assessment of the possible contribution from natural sources.     

Photochemical model calculations over Europe for two extended summer periods: 1985 and 1989. Model results and comparison with observations

Ozone concentrations over Europe have been calculated with the EMEP MSC-W ozone model for two extended summer periods: April–September 1985 and April–October 1989. The predicted monthly variations in both mean and elevated ozone levels are illustrated. The model is shown to compare satisfactorily with ozone data across nearly all the months studied, particularly in 1989. Modelled PAN and total airborne nitrate concentrations are also shown to compare favourably with the measurements of a Nordic measurement campaign in autumn 1989, although there is an unresolved discrepancy between the modelled and observed NO₂ at these sites. In addition, the model has now been used to estimate the effects of NO_x and volatile organic compound emission control on both mean and elevated ozone levels for 6 months in 1989.     

Calculation of long term averaged ground level ozone concentrations

Seasonal averaged ground level concentrations for O₃ have been calculated for The Netherlands by means of a two-layer Lagrangian long-range transport (LRT) model. The model includes emissions, nonlinear atmospheric chemistry, dry deposition, exchange between boundary layer (BL) and free troposphere (FT) and fumigation between a mixed layer and an aged smog layer. Concentrations of primary and secondary pollutants in the FT are obtained from a two-dimensional global model developed by Isaksen.In the reference calculation the modelled concentrations of Ox (sum of O₃ and NO₂) and O₃ are in fair agreement with measurements. The NO_x (sum of NO and NO₂) and NO₂ concentrations are under-estimated by the model but there is a good temporal correlation between calculated and measured concentrations. Validation of other components involved in the chemical scheme is hardly possible due to the paucity of measured data. It can only be stated that the results presented in this paper are not in disagreement with measured or modelled data presented in the literature.In a number of sensitivity runs the influence of European anthropogenic emissions of NO_x and volatile organic compounds (VOC) has been investigated. The calculations indicate that the influence of European emissions on the growing season, daytime averaged (May–September, 10–17 h) O₃ concentrations in The Netherlands is small. For European reductions in the order of tens of per cents a VOC emission reduction is more effective than a NO_x emission reduction in lowering the O₃ concentrations. For strong reductions (about 70%) VOC and NO_x are equally effective. The effects of the modelled underprediction of NO_x concentrations on the production of O₃ on a European scale are probably small. On a local scale the effects are more pronounced due to the NO/O₃ titration (photostationary equilibrium). Therefore, an empirical correction is applied on the modelled O₃ concentrations. After this correction, it is shown that daytime O₃ levels during the growing season increase when European NO_x emissions are reduced (2.0–7.7.% increase at 50% NO_x emission reduction). A reduction in VOC emission leads to decreasing O₃ levels (9% reduction for 40% VOC emission reduction, 16% reduction for 70% VOC emission reduction). For a combined reduction of both VOC and NO_x slightly decreasing ground level O₃ concentrations are expected.     

夏季长三角地区臭氧非线性响应曲面模型的建立及应用

2013年8月上旬,长三角地区发生了一次大范围高浓度臭氧污染事件.本研究基于WRF-CMAQ空气质量模型系统,结合长三角地区大气污染物排放清单,构建了臭氧与其前体物之间的非线性响应曲面模型(Response surface modeling,RSM).基于RSM探讨了长三角地区O_3化学的敏感性特征,分析了上海市O_3的来源并预测不同情景下O_3的变化,提出O_3污染的最优控制方案.研究结果表明,长三角地区夏季O3主控因素区域差别较大,上海环科院、杭州卧龙桥、南京玄武湖等城区点位属于VOC控制型;徐州铜山、合肥肥西、丽水青田等郊区属于NOx控制型.O_3的敏感性特征在不同浓度水平下也呈现较大差异,随着O_3浓度水平的升高,各地区NOx敏感性均有所增加.从区域来源来看,远距离传输对平日上海O_3贡献较大,占50%以上;而在O_3污染日,本地及区域贡献为72.1%,而远距离传输贡献下降至27.9%.快速预测了110组减排情景,表明在本地及区域前体物均减排70%的情况下,2013年8月上海O_3浓度能完全达标.     

Relationship of non-methane hydrocarbons and NOx to ozone formation in the atmosphere of Bahrain

The hourly air quality monitoring data for hydrocarbons, NO_x, and ozone were analyzed from two sites; one north of the industrial areas in Sitra and the other one located south on the east coast. The background levels of non-methane hydrocarbons at both sites were in excess of the U.S. federal ambient air quality standard of 0.24 ppm most of the time. The U.S. ozone air quality hourly standard of 0.12 ppm. however, was exceeded twice only at Sitra during high ambient NO _x concentrations greater than 0.15 ppm and high non-methane hydrocarbon levels of 10 ppm. The suitability of introducing the U.S. standard for non-methane hydrocarbons to the region is discussed.     

柴油/甲醇组合燃烧发动机的氮氧化物排放研究

在增压共轨发动机上采用柴油/甲醇组合燃烧(DMCC)方式进行了氮氧化物排放特性研究.对DMCC模式下NO x、NO、NO2等排放与纯柴油模式的对比分析表明:DMCC模式下的NO x排放比原机模式平均下降10%以上,NO平均下降幅度超过40%;采用DMCC模式后,NO2排放量都有明显大幅度的升高,并且NO2/NO比值呈现显著增大,平均高达100%以上.     

Fluxes of nitric and nitrous oxides from agricultural soils in a cool temperate climate

Fluxes of NO and N₂O from sandy loam soils cropped with winter wheat and a clay loam soil under ryegrass, with and without the addition of NH₄NO₃ fertilizer, were measured using static and dynamic chamber methods. Nitric oxide fluxes ranged from −0.3 (deposition) to 6.9 (emission) ng NO-N m⁻² s⁻¹. The corresponding N₂O flux ranged from 0 to 91 (emission) ng N₂O-N m⁻² s⁻¹. The NO flux was temperature dependent. Activation energies ranged from 40 to 81 kJ mol⁻¹. Nitric oxide and N₂O fluxes increased linearly with soil available nitrogen (NH₄ + NO₃). Emissions of NO and N₂O were not detectable from unfertilized ryegrass plots. Instead, nitric oxide was absorbed by the soil and vegetation at a maximum rate of 0.31 ng NO-N m⁻² s⁻¹. The aeration state of the soil controlled the relative rates of NO and N₂O emission. Nitric oxide was the major gas emitted from well aerated soils, conditions that favour nitrification. The NO/N₂O emission ratio was >100 for the coarse-textured sandy loam soil and the clay loam soil only during low rainfall periods. Nitrous oxide was the major gas emitted from less aerated soils, conditions that allowed denitrification to occur. The NO/N₂O emission ratio was <0.001 for the clay loam soil when rainfall was high and soils were wet. Extrapolation to the U.K. situation showed that agricultural land may account for 2–6% of the total annual NO_x emission and for 16–64% of the total annual N₂O emission in the U.K.     

The impact of changing regional emissions on precipitation chemistry in the eastern United States

From 1975 to 1987 a 19% change in SO₂ emissions a 16% change in NO_x emissions have occurred over the eastern and mid-western U.S. Six continental precipitation chemistry sites from the MAP3S network, plus the Hubbard Brook Experimental Forest, NH, show a direct relationship between emission levels and precipitation H⁺ and SO₄^2- concentrations, except for Penn State, PA. MAP3S sites at Illinois and Ohio, located closest to the major SO₂ source regions, demonstrates statiscally significant (P <0.05) linear regressions of SO₄^2- concentrations on SO₂ emissions. Whiteface Mt., NY, shows a weaker relationship (P <0.01), and Hubbard Brook shows the strongest relationship (P <0.01) between SO₂ emissions and SO₄^2- concentration in precipitation. No site shows a significant relationship (P <0.10) for NO_x emissions and NO₃⁻ concentrations in precipitation. Illinois, Ohio, Ithaca and Hubbard Brook show significant linear regressions of H⁺ concentrations on emissions of SO₂ + NO_x (P <0.10, 0.05, 0.01, and 0.01, respectively). Overall, for the entire region examined, decreasing SO₂ emissions levels appear to have decreased SO₄^2- concentrations with an efficiency of 74% ± 15% (s.e.). Decreasing SO₂ plus NO_x emissions (18%) have been accompanied by a decreasing H⁺ concentrations (18%) suggesting an efficiency of conversion of 100% ± 15% (s.e.) for the study region as a whole. While significant reductions in acid species have occured at Hubbard Brook, further reductions in excess of 50% of present deposition are necessary to protect acid-sensitive ecosystems.     

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.     

Hydrogen peroxide levels in Los Angeles: A screening-level evaluation

The major factors affecting the diurnal variation of gaseous hydrogen peroxide were studied using a one-dimensional vertical gas-phase chemistry/transport screening model. The model which included diurnal variations of the inversion layer, surface emissions, dry deposition of air pollutants, and meteorological conditions such as solar radiation, temperature, relative humidity and wind speed, was used to evaluate the influence of the ratio of NMHC/NO_x, the emission rates of NO_x and NMHC, the deposition velocity of H₂O₂, and the height of inversion layer on the ground level gaseous H₂O₂ concentrations. The model was found to yield reasonable agreement with field data from the Carbonaceous Species Methods Comparison Study at Glendora, California, in 11–21 August 1986. Specifically, model predictions and field results all indicated that during clear skies, ambient H₂O₂ concentration was highest at about early afternoon when O₃ concentration was highest and NO_x was lowest. It was concluded that the predicted gaseous H₂O₂ concentration is most sensitive to the emission rate of NO_x and the ratio of NHMC/NO_x, but it is less sensitive to the deposition velocity, height of inversion layer, and the emission rate of NMHC.     

Trends analysis of vegetation exposure indices in rural areas of the U.S.

In this work, statistical models based on a linear time term are tested to determine if they can adequately represent the behavior over time of indices that relate vegetation exposure to air pollutants at a large number of monitoring sites in the rural U.S. Three pollutants are addressed: ozone (O₃), sulfur dioxide (SO₂)and nitrogen dioxide (NO₂. The formulations selected to generate the values of the exposure indices were the sum of all hourly average concentrations (SUM0); in addition, for O₃, the sum of all hourly average concentrations weighted with a sigmoidal function, which assigned larger weights to the higher concentrations. The basic hourly average concentration data were selected from routine air monitoring stations of existing networks that met minimum criteria for quality assurance and data completeness. The statistical methodology used was based on a linear regression model which accounted for seasonality and changes in experimental procedures. An additional lag-one autoregressive term was added to the model for those stations which exhibited significant autocorrelation in the data, based on the Durbin-Watson statistic. Long-term analyses included data for 7 to 10 years; short-term analyses included data for 4 to 5 years. Results show that over rural areas of the U.S., these models do not adequately represent the behavior of vegetation exposure indices, both in the long-term and the short-term analyses; the majority of stations did not have statistically significant (5% level) coefficients for the term representing linear dependence on time. Emissions data for SO₂, NO_x and volatile organic compounds (VOC) over the same time period are also presented. Over the contiguous U.S., emissions between 1979 and 1987 have decreased by a maximum of 3%; emission changes for individual states have generally decreased between 1979 and 1987, but between 1983 and 1987 both increases and decreases have occurred.     

Calculation of long-term averaged and episodic oxidant concentrations for the Netherlands

Ground-level ozone and oxidant (sum of O₃ and NO₂) concentrations in The Netherlands are calculated during the growing season (May–September) by means of a Lagrangian long-range transport model. Two air parcels—one representative of the mixed layer, the other representative of the polluted layer above the mixed layer (aged smog layer)—are followed along 96 h back trajectories. Long-term averaged and 98 percentile values of hourly averaged concentrations are estimated on the basis of concentrations calculated for four arrival times per day for all days in the period considered.In a number of sensitivity runs the influence of European anthropogenic NO_x and VOC emissions on the oxidant concentrations in The Netherlands has been investigated. In general, the influence of European emissions on the 98-percentile values is 2–3 times as large as on the averaged concentrations. This indicates that long-term averaged concentrations more strongly depend on the concentrations in the free troposphere whereas the episodic concentrations are determined by photochemical production over Europe. VOC emission reduction is more effective in lowering episodic concentrations than NO_x emission reduction. For long-term averaged concentrations, however, NO_x and VOC emission reduction of 50% or more are nearly equally effective.     

基于CMAQ模式的自适应“nudging”源反演方法的中国主要污染区排放特征分析

中国中东部地区的空气污染主要集中在京津冀、长三角、珠三角、东北地区及汾渭平原等区域，各区域的污染排放特征各异.本文应用基于CMAQ（The Community Multiscale Air Quality）模式的自适应"nudging"源反演方法，反演中国中东部地区2016年12月—2017年1月逐日NO_x污染源，分析上述主要污染区的污染物排放强度空间分布特征，并与2016年MEIC（The Multi-resolution emission inventory for China）排放源进行比较，检验反演源的可靠性.结果表明，2016年冬季各个区域反演源NO_x排放强度空间分布特征与2016年MEIC排放源基本一致.京津冀地区高强度排放区域形成沿山前区域东北-西南走向的NO_x高强度排放带；长三角地区NO_x高强度排放区域位于常州、苏州、上海和湖州等城市构成的城市群；珠三角地区NO_x高强度排放区域位于以广州为中心的大范围城市群且排放强度呈现向四周逐渐降低的放射状分布；东北地区NO_x高强度排放区域空间分布特征呈现以城市为中心且稀疏分布；汾渭平原排放区域呈现以城市为中心且向峡谷中间集中分布，排放区域轮廓与汾渭平原狭长的新月状相符.     

High NO2/NOx emissions downstream of the catalytic diesel particulate filter: An influencing factor study

Diesel vehicles are responsible for most of the traffic-related nitrogen oxide (NO_x) emissions, including nitric oxide (NO) and nitrogen dioxide (NO₂). The use of after-treatment devices increases the risk of high NO₂/NO_x emissions from diesel engines. In order to investigate the factors influencing NO₂/NO_x emissions, an emission experiment was carried out on a high pressure common-rail, turbocharged diesel engine with a catalytic diesel particulate filter (CDPF). NO₂ was measured by a non-dispersive ultraviolet analyzer with raw exhaust sampling. The experimental results show that the NO₂/NO_x ratios downstream of the CDPF range around 20%–83%, which are significantly higher than those upstream of the CDPF. The exhaust temperature is a decisive factor influencing the NO₂/NO_x emissions. The maximum NO₂/NO_x emission appears at the exhaust temperature of 350°C. The space velocity, engine-out PM/NO_x ratio (mass based) and CO conversion ratio are secondary factors. At a constant exhaust temperature, the NO₂/NO_x emissions decreased with increasing space velocity and engine-out PM/NO_x ratio. When the CO conversion ratios range from 80% to 90%, the NO₂/NO_x emissions remain at a high level.     

大气NOx测量准确性问题分析

采用美国热电公司的NO-N02-NOx分析仪(Model 42i TL)和NOy分析仪(Model 42i NOy),在2011年1月-10月期间,对北京城市大气中的NO、NOx和NOy进行了连续在线测量.两台仪器对NO的测量结果具有较高的一致性(r＞0.998,p＜0.01),说明两台仪器测量精度基本一致.将NOy分析仪(Model 42i NOy)采样口处安装和不安装颗粒物过滤膜两种条件下测量的NOy结果与NO-NO2-NOx分析仪所测的NOx结果分别进行了相关性分析([NOy] =0.989x[NOx],R2 =0.993;[NOy] =1.134 ×[NOx],R2=0.959),得出以下两个结论:①以颗粒态硝酸盐为代表的颗粒物是造成NOx与NOy偏差的主要原因,其所占比例在10％左右;②目前Model 42i-TL所测NOx的浓度水平较真实值偏高,其测量值更接近气态NOy的浓度水平.为估算NO2测值被高估的程度(以2011年8月6日-15日观测数据为例),用扣除部分气态NOz物种(HONO、HNO3、PAN、PPN)的修正方法,推论出在夏季N02被高估约7％(R2=0.968).     

夏季城市大气O3浓度影响因素及其相关关系

利用2003年夏季济南市区近地面大气O₃、相关前体物和气象因素等观测数据,研究了O₃浓度的分布特征及时间变化规律,分析了7月份O₃与NO、NO₂和CO等前体物及太阳辐射和气温气象条件的相关性.结果表明,济南市区夏季O₃污染比较严重,观测期间各污染物O₃、NO、NO₂、NO_x和CO浓度都相对较高,昼间O₃与各前体物的浓度呈较好的负相关关系,与太阳辐射具有非常明显的相关性,而与气温的相关性不明显.根据以上分析结果,利用回归分析方法,建立了昼间O₃浓度与前体物、气象因子之间的相关模式,结果表明O₃浓度的计算值与观测值符合性较好.     

Lake Michigan Ozone Study (LMOS): Measurements from an instrumented aircraft

As part of the Lake Michigan Ozone Study, the NOAA instrumented King Air research aircraft made a series of flights over Lake Michigan during the summers of 1990 and 1991 to characterize the atmospheric conditions prevailing during times when O₃ concentrations exceeded the air quality standard. Most of the time, O₃ concentrations were within the normal range (40–70 ppbv) for the location and season, but higher concentrations were measured during the afternoon flights at several isolated locations. During three afternoon flights, high O₃ concentrations (> 120 ppbv) were observed along portions of the flight path; the highest 1-min average exceeded 160 ppbv. In two flights the highest O₃ concentrations were observed in the lower boundary layer over the eastern portion of the flight track; in one case the high concentrations were found over the western side of the lake throughout the boundary layer. The increased O₃ was accompanied by moderately increased SO₂ and NO_x (10–20 ppbv); outside the region of elevated O₃, the SO₂ and NO_x were less than 2–3 ppbv. The elevated zone concentrations were related to emissions from the urban region located near the southern and southwestern shores of Lake Michigan.     

北京大气中NO、NO2和O3浓度变化的相关性分析

臭氧（O₃）是城市污染大气中的首要光化学污染物,其变化规律与氮氧化物(NO_x=NO+NO₂)关系密切.采用49C臭氧分析仪和42CTL氮氧化物分析仪对北京城区O₃和NO_x浓度进行了连续观测,时间为2004-08～2005-07.结果显示,O₃和OX（O₃+NO₂）浓度在午后15:00左右出现峰值,NO_x呈双峰态日变化,在07:00和23:00左右出现峰值.不同季节污染物的浓度变化存在差异,O₃和NO_x浓度分别在夏季和冬季达到最大.NO_x浓度存在100×10^-9(体积分数)的“分界点”,NO_x低浓度时以NO₂为主,NO_x高浓度时NO占大部分.OX区域贡献和局地贡献存在明显的季节变化,前者主要受区域背景O₃的影响,在春季最大,后者主要受局地NO_x光化学反应的制约,在夏季最强,同时OX组分呈现显著的昼夜差异.     

Source-receptor relationships for wet SO42− and NO3− production

Precipitation chemistry data for the years 1982–1985 from 110 stations distributed across the continental U.S. and southern Ontario Province are used to describe the geographic distributions of SO₄²⁻ and NO₃⁻ in precipitation. Volume-weighted, wet SO₄²⁻ and NO₃⁻ concentrations, averaged over the 4 years of observation by season and annullly, show coherent patterns with maxima in the northeastern U.S. and southeastern Canada about ten times greater than the minima observed in the Intermountain and Pacific Northwest regions.Tests for empirical source-receptor relationships indicate that, in land areas with relatively low emissions of SO₂ and NO_x, the associations between wet SO₄²⁻ concentrations and SO₂ emissions and between wet NO₃⁻ concentrations and NO_x emissions within 560 km of each precipitation chemistry station are weak or nonexistent (r²⩽0.42). The remaining land areas show moderate to strong associations between SO₂ and SO₄²⁻ and NO_x and NO₃⁻ during the spring and summer, but only weak to nonexistent associations during the winter. The associations between emissions and concentrations, e.g. SO₂ and SO₄²⁻, are equally well represented by either a linear or a power law function. However, at the level of aggregation employed, the data do not substantiate a linear-proportional relationship between concentrations and anthropogenic emissions. Furthermore, emissions of SO₂ and NO_x are highly correlated, as are the emissions of RHC and NO_x.