Regression modelling of hourly NOx and NO2 concentrations in urban air in London

Based on hourly measurements of NO_x NO₂ and O₃ and meteorological data, an ordinary least squares (OLS) model and a first-order autocorrelation (AR) model were developed to analyse the regression and prediction of NO_x and NO₂ concentrations in London. Primary emissions and wind speed are the most important factors influencing NO_x concentrations; in addition to these two, reaction of NO with O₃ is also a major factor influencing NO₂ concentrations. The AR model resulted in high correlation coefficients (R > 0.95) for the NO_x and NO₂ regression based on a whole year's data, and is capable of predicting NO₂ (R = 0.83) and NO_x (R = 0.65) concentrations when the explanatory variables were available. The analysis of the structure of regression models by Principal Component Analysis (PCA) indicates that the regression models are stable. The results of the OLS model indicate that there was an exceptional NO₂ source, other than primary emission and reaction of NO with O₃, in the air pollution episode in London in December 1991.     

Analysis of NO,NO2, O3 and NOx concentrations measured at a green area of Buenos Aires City during wintertime

We analyse the air quality data measured at a green area of Buenos Aires City (Argentina) during 38 days in winter. We study the relationships between ambient concentrations of nitric oxide (NO), nitrogen dioxide (NO₂), ozone (O₃) and nitrogen oxides (NO_x=NO+NO₂). The variation of the level of oxidant (OX=O₃+NO₂) with the NO_x is obtained. It can be seen that the level of OX at a given location is made up of two contributions: one independent and another dependent on the NO_x concentration. The first one can be considered as a regional contribution, equivalent to the background O₃ concentration and the second one as a local contribution that depends on the level of primary pollution. Local oxidant sources may include direct NO₂ emissions, the reaction of NO with O₂ at high-NO_x levels, and the emission of species that promote the conversion of NO to NO₂. The final category of emissions may include the nitrous acid (HONO) that is emitted directly in vehicle exhaust. Finally, we present a diurnal variation of the local as well as regional contributions and the dependence of the last one on wind direction.     

Partitioning, sources and variability of regional and local oxidant (OX = O3 + NO2) in a coastal rural area in the southwest of Iberian Peninsula

The purpose of this work is to investigate the behaviour and variability of oxidant levels (OX?=?NO₂?+?O₃), for the first time, in a rural coastal area in the southwest of the Iberian Peninsula, affected by several air masses types. Detailed database (built-up over the years 2008 to 2011, and containing around 500,000 data) from the Atmospheric Sounding Station “El Arenosillo” was used. The observed daily cycles of NO _x and OX were influenced by air masses coming from industrial and urban area. It can be seen that the concentration of OX is made up of a NO _x -independent ‘regional’ contribution (i.e. the O₃ background), and a linearly NO _x -dependent ‘local’ contribution from primary emissions, such as traffic. The local emission is very low in this area. Also, the regional contribution is similar to unpolluted sites and presents seasonal variation, being higher in May. However, our measurements showed that the proportion of OX in the form of NO₂ increases with the increase in NO _x concentration during the day. The higher proportion of NO₂ observed at night must be due to the conversion of NO to NO₂ by the NO?+?O₃ reaction. With regards to the source of the local NO _x -dependent contribution, it may be attributed to industrial emission, or the termolecular reaction 2NO?+?O₂?=?2NO₂, at high-NO _x levels and stagnant air during several days. Finally, we estimated the photolysis rate of NO₂, J _NO2, an important key atmospheric reaction coupled with ozone. We also present surface plots of annual variation of the daily mean NO _x and OX levels, which indicate that oxidants come from transport processes instead of local emissions associated as local photochemistry.     

北京市交通道路空气中NO_x的污染现状及时空变化规律研究

基于2008年及2009年分4个季节对北京市3种类型道路(开阔型、交叉路口型和峡谷型)空气中的NOx的现场监测结果,分析了3种类型道路空气中NOx的污染现状和时空变化规律及影响因素。实验结果表明,昼间北京市各类型街道空气中NOx浓度呈早晚浓度高、中午浓度低的变化规律,NOx浓度随季节和车流量变化较明显。交通道路空气中NO占NOx的分担率高,且有较好的相关性,而NO2分担率较低,与NOx相关性较差。     

石家庄市道路交通环境NO_x污染水平及ARMA模型预测

选择石家庄市区代表性路段作为研究对象,对其交通环境空气中NOx的污染水平进行现状监测。基于Matlab软件建立拟合模型,对下一时期的NOx污染趋势进行预测。结果表明,石家庄市交通环境中NOx小时浓度介于0.047~0.237 mg/m3之间,呈早晚高,且下午明显低于上午的日变化规律;NOx日均浓度介于0.076~0.211 mg/m3之间,其浓度与车流量呈明显的正相关性。利用matlab软件建立的ARMA模型能够较好地预测道路交通环境空气中NOx的浓度变化趋势。     

改进钒基SCR脱硝催化剂的抗碱金属中毒性能

以锐钛矿型二氧化钛和钛钨粉(5%WO3-TiO2)为载体,制备了系列钒和钨负载量不同的钒钛催化剂,考察碱金属和碱土金属(钾、钠和钙)对催化剂在氨选择性催化还原(NH3-SCR)氮氧化物反应中催化活性的影响。钾、钠和钙对钒钛催化剂的中毒影响大小顺序为钾钠钙。提高钒钛催化剂中钒的含量可显著提高催化剂的SCR活性和抗碱金属中毒性能,但高钒负载量(4.5%V2O5)造成催化剂氮气选择性明显下降,氧化亚氮生成显著增加。钨的添加有利于提高钒钛催化剂的低温活性和抗碱金属中毒性能,对氮气选择性无明显影响。     

燃煤烟气低温SCR脱硝中试研究

低温选择性催化还原(SCR)脱硝是国内外脱硝技术研发的热点,但目前主要集中在实验室小试范围,无法完全反映催化剂在实际烟气中的运行状况。在30 t/h循环流化床燃煤锅炉脱硫除尘装置后建设了2 000~5 000 m3/h的SCR脱硝中试装置,经系统研究发现,中试使用的蜂窝式催化剂对SO2和NO具有很强的吸附能力,且反应温度、喷氨速率和气体空速均会影响催化脱硝效率。为期5 d的连续运行实验结果表明,催化剂的脱硝效率一直稳定在30%~50%,并未发现明显的失活,这证明设计除雾除尘器、较大的混合器、混合器与反应器间较长的管路均有利于缓解催化剂因SO2、H2O和飞灰中的碱性金属导致的失活。     

Behaviour and variability of local and regional oxidant levels (OX = O3 + NO2) measured in a polluted area in central-southern of Iberian Peninsula

The purpose of this work is to contribute to the understanding of the photochemical air pollution in central-southern of the Iberian Peninsula, analysing the behaviour and variability of oxidant levels (OX?=?O₃?+?NO₂), measured in a polluted area with the highest concentration of heavy industry in central Spain. A detailed air pollution database was observed from two monitoring stations. The data period used was 2008 and 2009, around 210,000 data, selected for its pollution and meteorological statistics, which are very representative of the region. Data were collected every 15 min, however hourly values were used to analyse the seasonal and daily ozone, NO, NO₂ and OX cycles. The variation of OX concentrations with NO _x is investigated, for the first time, in the centre of the Iberian Peninsula. The concentration of OX was calculated using the sum of a NO _x -independent ‘regional’ contribution (i.e. the O₃ background), and a linearly NO _x -dependent ‘local’ contribution. Monthly dependence of regional and local OX concentration was observed to determine when the maximum values may be expected. The variation of OX concentrations with levels of NO _x was also measured, in order to pinpoint the atmospheric sources of OX in the polluted areas. The ratios [NO₂]/[OX] and [NO₂]/[NO _x ] vs. [NO _x ] were analysed to find the fraction of OX in the form of NO₂, and the possible source of the local NO _x -dependent contribution, respectively. The progressive increase of the ratio [NO₂]/[OX] with [NO _x ] observed shows a greater proportion of OX in the form of NO₂ as the level of NO _x increases. The higher measured values in the ratio [NO₂]/[NO _x ] should not be attributed to NO _x emissions by vehicles; they could be explained by industrial emission, termolecular reactions or formaldehyde and HONO directly emitted by vehicles exhausts. We also estimate the rate of NO₂ photolysis, J _NO2?=?0.18–0.64 min^?1, a key atmospheric reaction that influence O₃ production and then the regional air quality. The first surface plot study of annual variation of the daily mean oxidant levels, obtained for this polluted area may be used to improve the atmospheric photochemical dynamic in this region of the Iberian Peninsula where there are undeniable air quality problems.     

Ground level ozone concentrations and its association with NOx and meteorological parameters in Kathmandu valley, Nepal

This paper summarizes the results of a yearlong continuous measurements of gaseous pollutants, NO, NO₂, NO_x and O₃ in the ambient air at Kathmandu valley. Measured concentration of the pollutants in study area is a function of time. NO, NO₂ and O₃ peak occurred in succession in presence of sunlight. At the time of maximum O₃ concentration most of the NO_x are utilized. The diurnal cycle of ground level ozone concentrations, revealed mid-day peak with lower nocturnal concentrations and inverse relationship exists between O₃ and NO_x, which are evidences of photochemical O₃ formation. The observed ground level ozone during monsoon is slight lower than the pre-monsoon value. Further, lack of rainfall and higher temperature, solar radiation in the pre-monsoon have given rise to the gradual build up of ozone and it is lowest during winter. Ground level ozone concentrations measured during bandha (general strike) and weekend are 19% and 13% higher than those measured during weekdays. The most effective ozone abatement strategy for Kathmandu Valley may be control of NO_x emissions.     

Regional NOx emission inversion through a four-dimensional variational approach using SCIAMACHY tropospheric NO2 column observations

In this paper, the NOx emission scaling factors applied over the 2001 National Emissions Inventory (NEI) are estimated through a four-dimensional variational (4D-Var) approach using SCIAMACHY (Scanning Imaging Absorption spectroMeter for Atmospheric CHartographY) tropospheric NO₂ columns measured during summer 2004. In the “top-down” approach, two-month average NO₂ columns are assimilated into a regional chemical transport model (CTM), STEM, using different assimilation setups. In a basic setup, NOx emissions are adjusted by assimilating the NO₂ columns. A more general setup of emission inversion allows the initial O₃ concentrations be adjusted along with the NOx emissions. A final case is set up to assimilate both the NO₂ columns and O₃ measurement from various platforms while allowing adjustments of both the NOx emissions and the initial O₃ concentrations. It is found that the addition of O₃ measurements did not improve the NOx emission inversion. With the NOx emission at surface and upper levels being adjusted separately, results from four cases show that the elevated NOx emission reduction ranges from 8.9% to 11.4%, and the surface NOx emission reduction is up to 6.6%. All the cases show NOx emission reduction in Ohio valley and Washington, District of Columbia areas.     

原位水解生成的羟基氧化铁凝聚吸附除磷效能与机制简

将不同摩尔比Fe³⁺与OH^-（[Fe³⁺]：[OH^-]=1：0、1：1、1：2和1：3）反应获得原位水解生成的羟基氧化铁（in situ FeO_xH_y），研究了具有不同水解程度的羟基氧化铁对凝聚吸附除磷效能与机制。研究显示，In situ FeO_xH_y对磷的去除率随铁投量增大而升高，且均在中性pH范围内具有最佳除磷效果；在相同铁投量条件下，磷去除率随着[OH^-]：[Fe³⁺]的升高而降低；当体系碱度较低时（pH<6），引入OH^-可促进Fe³⁺水解而提高除磷效果。4种羟基氧化铁均可在15 s内可快速吸附磷，且吸附过程符合准二级动力学模型；Freundlich模型均可很好地描述磷在4种羟基氧化铁表面的吸附行为。磷酸盐吸附后，In situ FeO_xH_y表面Zeta电位明显降低，且[Fe³⁺]：[OH^-]为1：0的羟基氧化铁降低最为显著。结合MINITEQ计算软件磷酸盐、铁盐形态分析结果显示，对于碱度较低的体系，通过投加一定量OH^-可促进Fe³⁺水解，进而使得其更易与水中H₂PO₄^-与HPO₄^2-结合，生成具有多核羟基的磷酸铁络合物，进而提高除磷效果。     

O3/H2O2处理嘧啶废水的研究

采用O3/H2O2法对嘧啶废水进行处理,考察了不同反应条件对嘧啶和COD去除率的影响,并对O3/H2O2降解嘧啶的反应机制和动力学进行了初步探讨.实验结果表明,在pH值为11,反应时间为70 min,O3流量为4g/h,H2O2投加量为50 mmol/L的条件下,废水的嘧啶和COD的去除率分别达到86.46%和74.9...     

钛基IrO2-SnO2电极在烟气海水脱硫恢复系统中的应用

采用浸渍-热分解法制备了含IrOx-TiO2中间层的IrO2-SnO2电极,得到的电极具有较高的析氯电催化活性和较强的稳定性,并通过电化学氧化法对Na2SO3海水脱硫模拟液进行处理,考察了电流密度、温度、pH值和电解时间等电解工艺参数对Na2SO3去除率和化学需氧量COD的影响.结果表明,在电流密度为200 mA/cm...     

Sources and processes affecting concentrations of PM10 and PM2.5 particulate matter in Birmingham (U.K.)

Hourly average concentrations of PM₁₀ and PM_2.5 have been measured simultaneously at a site within Birmingham U.K. between October 1994 and October 1995. Comparison of PM₁₀ and NO_x data with two other sites in the same city shows comparable summer and winter mean concentrations and highly significant inter-site correlations for both hourly and daily mean data. Over a four-month period samples were also collected for chemical analysis of sulphate, nitrate, chloride, ammonium and elemental and organic carbon. Analysis of the data indicates a marked difference between summer and winter periods. In the winter months PM_2.5 comprises about 80% of PM₁₀ and is strongly correlated with NO_x indicating the importance of road traffic as a source. In the summer months, coarse particles (PM₁₀−PM_2.5) account for almost 50% of PM₁₀ and the influence of resuspended surface dusts and soils and of secondary particulate matter is evident. The chemical analysis data are also consistent with three sources dominating the PM₁₀ composition: vehicle exhaust emissions, secondary ammonium salts and resuspended surface dusts. Coarse particles from resuspension showed a positive dependence on windspeed, whilst elemental carbon derived from road traffic exhibited a negative dependence.     

铜-胺改性ZSM-5吸附剂的制备及其对NOx的净化机理

以ZSM-5分子筛粉体为原料，成型后负载铜盐和有机胺改性，制备出一种高效脱除氮氧化物的吸附剂。通过改变铜盐、有机胺的含量以及铜盐活化温度使吸附剂的性能得到优化，在实验条件下（NO₂初浓度1 000 mg/m³，气流2.7 L/min）床层对NO₂动态吸附的透过时间由改性前的3 min提高到90 min，并使NO气体的释放得到有效减缓。通过动态吸附实验研究了NO释放时间在负载前后的变化，通过X射线光电子能谱（XPS）和红外分析（FTIR）研究了吸附剂表面铜元素、有机基团等在吸附前后的变化规律，提出了可能的净化机理。     

中小型工业窑炉NO_x废气的净化技术与应用

介绍了中小型工业窑炉生产过程中排放NOx的现状,并针对NOx的治理问题,从工程应用角度,简述了湿法和干法净化NOx的原理和化学反应过程。讨论了NOx排放特性和NOx废气中NO2/NOx比例的问题。提出了影响NOx治理的主要因素,包括吸收剂、吸附剂、催化剂和设备的部分应用参数,并结合工程实例指出工程需要注意的问题。介绍了多项采用湿法和干法净化NOx的工程应用项目,丰富了中小工业窑炉NOx废气的治理的实践经验,为中小工业窑炉排放NOx治理奠定了基础。     

微波辐射Bi2O3/沸石-H2O2体系降解废水中的硝基苯

研究了微波辐射下，以负载于沸石上的三氧化二铋为催化剂，以双氧水为氧化剂的催化氧化体系处理硝基苯工艺。通过单因素实验法，从反应催化剂负载量、pH、双氧水用量、微波功率、反应时间、催化剂用量等方面初步考察了硝基苯在该体系中的催化氧化效果。在氧化铋负载量3%（质量比），pH=2，2 mL 30%双氧水，火力为中火，催化剂投加量为0.7 g，反应2 min，对降解过程所得的中间产物和终产物进行了分析。结果表明，该体系对硝基苯的去除率能够达到99.2%，COD去除率为73.91%。     

High NOx levels and lack of ozone in downtown Caracas

An evaluation of the NO, NO₂ and O₃ concentrations in downtown Caracas atmosphere at two different heights (1.5 and 56 m ) during the dry and wet season was performed.The qualitative variation of NO and NO₂ concentrations throughout the day was the same for all conditions. The profiles are explained considering the automobile emissions and the fates by photochemical reactions and dispersion. The daily mean averages for NO_x exceed all available air quality standards, making the downtown Caracas air polluted with these compounds at harmful levels.The O₃ concentrations are lower than the natural background levels practically all day long for all conditions. This lack of O₃ is explained mainly by the very high continuous NO emissions occuring in Caracas. NO reacts very fast with O₃ consuming all the O₃ produced by photochemical reactions. Possible health implications of the low O₃ levels are pointed out.     

Overestimation of urban nitrogen dioxide by passive diffusion tubes: a comparative exposure and model study

A detailed comparative trial of passive diffusion tubes (PDT) for measurement of NO₂ in urban air has been undertaken in Edinburgh, UK. Acrylic, foil-wrapped and quartz tubes were exposed in parallel for 1-week and 4-week periods at three urban sites equipped with continuous analysers for NO, NO_x and O₃. Standard acrylic PDTs significantly overestimated NO₂ concentrations relative to chemiluminescence analysers, by an average of 27% over all sites for 1-week exposures. No significant difference was observed between standard and foil-wrapped acrylic tubes (both UV blocking). The mean ratio between quartz (UV transmitting) tubes and chemiluminescence analysers was 1.06. Quartz PDT data suggest a tendency for in situ photolysis to offset (but in a non-quantifiable way) the effect of chemical overestimation. The 4-week exposures yielded systematically lower NO₂ concentration than average NO₂ from four sequential 1-week exposures over the same period. The reduction in the apparent NO₂ sampling rate with time mostlikely arises from in situ photolysis of trapped NO₂. Hourly NO₂, NO and O₃ data for 20 1-week exposures were used as input to a numerical model of diffusion tube operation incorporating chemical reaction between co-diffusing NO and O₃ within the tube. The mean calculated overestimation of 22% for NO₂ from the PDT model simulations is close to the average difference between acrylic PDT and analyser NO₂ concentrations (24% for the same exposure periods), showing that within-tube chemistry can account for observed discrepancies in NO₂ measurement between the two techniques. Overestimation by PDT generally increased as average NO₂/NO_x ratios decreased. Accurate quantitative correction of PDT measurements is not possible. Nevertheless, PDT NO₂ concentrations were correlated with both analyser NO₂ and NO_x suggesting that acrylic PDTs retain a qualitative measure of NO₂ and NO_x variation at a particular urban location.     

Assessment of natural components of PM10 at UK urban and rural sites

Proposals from the European Commission have raised the possibility that Member States may be able to subtract the concentrations of natural components of airborne particulate matter from measured concentrations when evaluating compliance with EU Limit Values. By applying the pragmatic mass closure model [Harrison et al., 2003. A pragmatic mass closure model for airborne particulate matter at urban background and roadside sites. Atmospheric Environment 37, 4927–4933] to chemical composition data for PM₁₀, it has been possible to estimate the concentrations of natural sea salt, strongly bound water and secondary organic carbon (which is assumed wholly biogenic) to the measured mass of PM₁₀. Because of the difficulty in distinguishing between natural and anthropogenic crustal dusts, the contribution of natural windblown dust and soil has not been accounted for. When the natural components are estimated for two urban and one rural site in the UK, the long-term mean PM₁₀ concentration is reduced by between 5.2 and 7.3 μg m⁻³. The number of exceedences of the 50 μg m⁻³ 24-h limit value falls dramatically from 54 to 21 (from a total of 291 days) at an urban street canyon site, 7 to 3 (n=292 days) at an urban background site and from 8 to 0 (n=241 days) at a rural site when using gravimetric PM₁₀ concentrations. The calculations have also been performed using PM₁₀ concentrations measured by TEOM increased by a factor of 1.3 as recommended by the European Commission as an interim means of estimating gravimetric equivalency, and the number of exceedences of the 24-h limit value fell from 92 to 47 (from a total of 291 days) at the urban street canyon site, from 11 to 3 (n=292 days) at the urban background site and from 6 to 3 (n=241) at the rural site. Clearly, therefore, application of this proposed measure would make a very major difference to the likelihood of compliance or otherwise with the 24-h limit value for PM₁₀.