Application of CALINE4 to roadside NO/NO2 transformations

The CALINE4 roadway dispersion model has been applied to concentrations of NO_x and NO₂ measured near Gandy Boulevard in Tampa, FL (USA) during May 2002. A NO_x emission factor of 0.86 gr mi⁻¹ was estimated by treating NO+NO₂ (NO_x) as a conserved species and minimizing the differences between measured and calculated NO_x concentrations. This emission factor was then used to calculate NO₂ concentrations using the NO/NO₂ transformation reactions built into CALINE4. A comparison of measured and calculated NO₂ concentrations indicates that for ambient O₃ concentrations less than 40 ppb the model under-predicts the chemical transformation of NO. The enhanced transformation of NO may be due to reactions of NO with oxidants such as peroxy radicals that are present either in the atmosphere or in vehicle exhaust.     

Modeling and monitoring of CO,NO and NO2 in a modern townhouse

Mass-balance models for indoor concentrations of CO, NO and NO₂ were applied to an energy-efficient townhouse. Model parameters included source emission rates, infiltrating airflows, and, for NO₂, loss rate coefficients. Emission factors for CO, NO and NO₂ were estimated for each of the gas-fired appliances in the house. Airflows were estimated using sulfur hexafluoride (SF₆) decay techniques. Loss rates for NO₂ were calculated as the difference between NO₂ removal rates and estimated air exchange rates; CO and NO concentrations decayed at a rate not significantly different than that for SF₆. Comparing model predictions with measured concentrations yielded differences averaging 17% for CO and NO, and 28% for NO₂.     

Seasonal evolutions of ozone (O3) and its nitrogen precursors (NO, NO2) in urban Sfax (Tunisia)

Seasonal evolution of ozone (O3) and its nitrogen precursors (NO, NO2) in downtown Sfax (Tunisia) was monitored. Nitrogen oxides are shown to be closely related to local vehicle sources. Seasonal ozone levels, however, are shown to be dependent on regional meteorological conditions. High ozone levels are due to the effect of anticyclones and stratosphere intrusions (cut-off lows). Low levels are associated with cyclonic conditions of small vertical range of motion. Other than these particular conditions, ozone levels are shown to be relatively higher in fall and winter seasons, characterised by a very steady atmosphere. Overall, the examined meteorological conditions, the ozone concentrations observed in downtown Sfax are characterised by clear day/night cycles, which can be explained by the significant ventilation of the region.     

UV Fourier transform measurements of tropospheric O3, NO2, SO2, benzene, and toluene.

Using the differential optical absorption spectroscopy (DOAS) technique and a Fourier transform spectrometer, NO2, SO2, O3, benzene. and toluene were measured during three measurement campaigns held in Brussels in 1995, 1996, and 1997. The O3 concentrations could be explained as the results of the local photochemistry and the dynamical properties of the mixing layer. NO2 concentrations were anti-correlated to the O3 concentrations, as expected. SO2 also showed a pronounced dependence on car traffic. Average benzene and toluene concentrations were, respectively 1.7 ppb and between 4.4 and 6.6 pbb, but high values of toluene up to 98.8 ppb were observed. SO2 concentrations and to a lesser extent, those of NO2 and 03, were dependent on the wind direction. Ozone in Brussels has been found to be influenced by the meteorological conditions prevailing in central Europe. Comparisons with other measurements have shown that 03 and SO2 data are in general in good agreement, but our NO2 concentrations seem to be generally higher.     

Analysis of air quality data near roadways using a dispersion model

We used a dispersion model to analyze measurements made during a field study conducted by the U.S. EPA in July–August 2006, to estimate the impact of traffic emissions on air quality at distances of tens of meters from an eight-lane highway located in Raleigh, NC. The air quality measurements consisted of long path optical measurements of NO at distances of 7 and 17 m from the edge of the highway. Sonic anemometers were used to measure wind speed and turbulent velocities at 6 and 20 m from the highway. Traffic flow rates were monitored using traffic surveillance cameras. The dispersion model [Venkatram, A., 2004. On estimating emissions through horizontal fluxes. Atmospheric Environment 38, 2439–2446] explained over 60% of the variance of the observed path averaged NO concentrations, and over 90% of the observed concentrations were within a factor of two of the model estimates.Sensitivity tests conducted with the model indicated that the traffic flow rate made the largest contribution to the variance of the observed NO concentrations. The meteorological variable that had the largest impact on the near road NO concentrations was the standard deviation of the vertical velocity fluctuations, σ_w. Wind speed had a relatively minor effect on concentrations. Furthermore, as long as the wind direction was within ±45° from the normal to the road, wind direction had little impact on near road concentrations. The measurements did not allow us to draw conclusions on the impact of traffic-induced turbulence on dispersion. The analysis of air quality and meteorological observations resulted in plausible estimates of on-road emission factors for NO.     

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.     

Absorption of NO and NO2 in Caprolactam Tetrabutyl Ammonium Halide Ionic Liquids

ABSTRACT

To explore environmentally benign solvents for the absorption of NO and NO₂, a series of caprolactam tetrabutyl ammonium halide ionic liquids were synthesized. The solubility of NO and NO₂ was measured at temperatures ranging from 298.2 to 363.2 K and atmospheric pressure, and the following trend in the solubility of NO and NO₂ in ionic liquids with various halide anions was observed, respectively: F > Br > Cl and Br > Cl > F. Moreover, as the temperature increased from 308.15 to 363.15 K and the mole ratio of caprolactam increased from 2:1 to 6:1, the solubility of NO increased. Alternatively, the solubility of NO₂ decreased as the temperature increased from 298.15 to 363.15 K, and the mole ratio of caprolactam increased from 2:1 to 6:1. The absorption and desorption of NO and NO₂ was practically reversible in the ionic liquids, which was characterized by nuclear magnetic resonance. The method, which is at least partially reversible, offers interesting possibilities for the removal of NO and NO₂.

IMPLICATIONS Basic ionic liquids with amino groups were synthesized and used to capture CO₂, SO₂, and H₂S, and to promote hydrogenation of CO₂. In this paper, the authors used caprolactam tetrabutyl ammonium halide ionic liquid (IL) as absorbing medium in which NO_x could be absorbed. NO_x desorbed from the absorbent could be efficiently reduced by right catalysts at high temperature. The absorbed NO and NO₂ gas could be desorbed at higher temperature, allowing the ionic liquids to be reused several times without loss of capability. It was believed that caprolactam tetrabutyl ammonium bromide (CPL-TBAB) ILs may be useful for NO_x removal reagent for pollution control.     

On the origins of night-time NO at a rural measurement site

Mixing ratios for NO and NO₂ were measured during 1980/1981 at Deuselbach, a rural site in Germany. The data are analyzed with regard to the occurrence of nocturnal NO signals and their origins. Anthropogenic influences arising from road traffic and home heating activities are identified by their dependence on wind direction. An additional non-directional component is found to exist. It shows up most frequently in summer and when it occurs, the NO mixing ratio increases with rising temperature indicating a biological origin of night-time NO. The temporal behavior of night-time NO is usually correlated with that of CO₂ but anticorrelated to that of O₃. This shows that NO is brought upwards to the air intake of the NO_x monitor from lower levels and that the source of the non-directional component of nocturnal NO is the earth's surface. The release of NO from soils is known from other work and this process is probably also responsible for the present observations. A flux estimate agrees with soil fluxes reported by other authors. The accumulation of NO in the surface air layer under stagnant conditions leads to the appearance of a morning peak of NO after sunrise when increased vertical mixing brings NO rich air up to the monitoring level. During summer, the morning peak may override the NO peak expected to occur at noon due to the photodissociation of NO₂.     

Meteorological variability in NO2 and PM10 concentrations in the Netherlands and its relation with EU limit values

The extent of the exceedance of the EU limit values for nitrogen dioxide (NO₂) and particulate matter (PM₁₀) concentrations within the Netherlands is expected to decrease significantly, in the coming years. Whether limit values will actually be exceeded, in the next decade, depends not only on European, national and local policies, but also on the effects of inevitable interannual meteorological fluctuations. An analysis of model calculations and measurements yields variations (1 sigma) in the annual average concentration of about 5% for NO₂ and 9% for PM₁₀, due to meteorological fluctuations. These deviations from long-term average concentrations affect assessments of future levels, set against limit values. For instance, an NO₂ concentration of 39 μg m^?3, estimated for a given year with long-term average meteorology, indicates that it is likely (chance >66%) that the limit value of 40 μg m^?3 will not be exceeded in that particular year. At the same time, the estimation also indicates, for example, that this situation is unlikely (change <33%) to continue for three years in a row. However, with an estimated concentration of 38 μg m^?3, it is likely that the limit value will not be exceeded for three years in a row. The limit value for the daily average PM₁₀ concentration is equivalent to an annual average of about 32 μg m^?3. This threshold is unlikely to be exceeded for three years in a row, when an annual average concentration of 29 μg m^?3 is estimated. Interannual variations in concentrations of NO₂ and PM₁₀ are linked to large-scale meteorological fluctuations. Therefore, similar results can be expected for other European countries.     

Seasonal patterns of ascorbate in the needles of Scots Pine (Pinus sylvestris L.) trees: correlation analyses with atmospheric O3 and NO2 gas mixing ratios and meteorological parameters

In the present field study the role of ascorbate in scavenging the harmful atmospheric trace gases O3 and NO2 was examined. For this purpose ascorbate contents were determined in needles of adult Scots pine trees (Pinus sylvestris L.) during three consecutive years. Ascorbate contents were correlated with ambient tropospheric O3 and NO2 concentrations and with meteorological parameters. The results showed a strong correlation of atmospheric O3 but not of atmospheric NO2 concentrations with the apoplastic content of ascorbate during the seasonal course. Ascorbate contents in needle extracts did not correlate with ambient trace gas concentrations. In the apoplastic space, but not in needle extracts ascorbate contents correlate highly significantly with global radiation. From these results it is assumed that apoplastic ascorbate in Scots pine needles is adapted to the actual atmospheric O3 concentration to mediate immediate detoxification of O3, while the atmospheric O3 concentration itself is largely dependent on light intensity.     

Evaluation of the CAR-FMI model against measurements near a major road

A field measurement campaign was conducted near a major road in southern Finland from September 15 to October 30, 1995. The concentrations of NO, NO₂ and O₃ were measured simultaneously at three locations, at three heights (3.5, 6 and 10 m) on both sides of the road. Traffic densities and relevant meteorological parameters were also measured on-site. We have compared measured concentration data with the predictions of the road network dispersion model CAR-FMI, used in combination with a meteorological pre-processing model MPP-FMI. In comparison with corresponding results presented previously in the literature, the agreement of measured and predicted datasets was good, as measured using various statistical parameters. For all data (N=587), the index of agreement (IA) was 0.83, 0.82 and 0.89 for the measurements of NO_x, NO₂ and O₃, respectively. The IA is a statistical measure of the correlation of the predicted and measured time series of concentrations. However, the modelling system overpredicts NO_x concentrations with a fractional bias FB=+13%, and O₃ concentrations with FB=+8%, while for NO₂ concentrations FB=−2%. We also analyzed the difference between model predictions and measured data in terms of meteorological parameters. Model performance clearly deteriorated as the wind direction approached a direction parallel to the road, and for the lowest wind speeds. The range of variability concerning atmospheric stability, ambient temperature and the amount of solar radiation was modest during the measurement campaign. As expected, no clear dependencies of model performance were therefore detected in terms of these parameters. The experimental dataset is available for the evaluation of other roadside dispersion models.     

Broadband UV spectroscopy system used for monitoring of SO2 and NO emissions from thermal power plants

A gas monitoring system based on broadband absorption spectroscopic techniques in the ultraviolet region is described and tested. The system was employed in real-time continuous concentration measurements of sulfur dioxide (SO₂) and nitric oxide (NO) from a 220-ton h^?1 circulating fluidized bed (CFB) boiler in Shandong province, China. The emission coefficients (per kg of coal and per kWh of electricity) and the total emission of the two pollutant gases were evaluated. The measurement results showed that the emission concentrations of SO₂ and NO from the CFB boiler fluctuated in the range of 750–1300 mg m^?3 and 100–220 mg m^?3, respectively. Compared with the specified emission standards of air pollutants from thermal power plants in China, the values were generally higher for SO₂ and lower for NO. The relatively high emission concentrations of SO₂ were found to mainly depend on the sulfur content of the fuel and the poor desulfurization efficiency. This study indicates that the broadband UV spectroscopy system is suitable for industrial emission monitoring and pollution control.     

Neural network modelling and prediction of hourly NOx and NO2 concentrations in urban air in London

Multilayer perceptron (MLP) neural networks were trained to model hourly NO_x and NO₂ pollutant concentrations in Central London from basic hourly meteorological data. Results have shown that the models perform well when compared to previous attempts to model the same pollutants using regression based models. This work also illustrates that MLP neural networks are capable of resolving complex patterns of source emissions without any explicit external guidance.     

The electrochemical selective reduction of NO using CoSe2@CNTs hybrid

Converting the NO from gaseous pollutant into NH₄ ⁺ through electrocatalytical reduction using cost-effective materials holds great promise for pollutant purifying and resources recycling. In this work, we developed a highly selective and stable catalyst CoSe₂ nanoparticle hybridized with carbon nanotubes (CoSe₂@CNTs). The CoSe₂@CNTs hybrid catalysts performed an extraordinary high selectivity for NH₄ ⁺ formation in NO electroreduction with minimal N₂O production and H₂ evolution. The specific spatial structure of CoSe₂ is conductive to the predominant formation of N-H bond between the N from adsorbed NO and H and inhibition of N-N formation from adjacent adsorbed NO. It was also the first time to convert the coordinated NO into NH₄ ⁺ using non-noble metal catalysis. Moreover, the original concept of employing CoSe₂ as eletrocatalyst for NO hydrogenation presented in this work can broaden horizons and provide new dimensions in the design of new highly efficient catalysts for NH₄ ⁺ synthesis in aqueous solution.

     

Dynamic NO adsorption characteristics of iron-treated activated carbon fibers

The breakthrough curve for NO adsorption on the activated carbon fibers treated in iron salt solutions was determined. They can adsorb much more NO than granular activated carbon by a factor of more than 10 from a flowing 300 ppm NO-N₂ mixed gas at 100°C and 20 ml min⁻¹; the most effective one of the iron-treated carbon fibers of 0.2 g is able to reduce the NO concentration from 300 ppm to 30 ppm. These adsorbents can adsorb the same amount of NO from even a 300 ppm NO-500 ppm SO₂-10% CO₂-10% H₂O-1% O₂-N₂ mixed gas.     

A Review of Techniques Available for Estimating Short-Term NO2 concentrations

The Environmental Protection Agency is reviewing the need for a short-term NO₂ standard based on an averaging time of three hours or less. State Implementation plans and New Source Reviews will require air quality simulation techniques capable of estimating ambient NO₂ concentrations. There is a need for multi-source (urban) models and for point source models.

A review of currently available techniques for the estimation of NO₂ concentrations resulting from NO_x point sources is presented. The available methods include simple screening techniques and refined reactive plume models. The screening techniques first use a standard gaussian dispersion model to estimate the maximum 1 hr NO_x concentration caused by the source. The second step involves estimating the fraction of this NO* concentration occurring as NO₂.

Reactive plume models numerically simulate the simultaneous effects of dispersion and chemistry on NO₂ concentrations. Organic as well as inorganic reactions are incorporated. Reactive plume models should be used, where screening techniques indicate the potential for violation of the NO₂ standard.

Current generation reactive plume models neglect the effect of turbulent concentration fluctuation on NO₂ formation and use inappropriately large dispersion coefficients to estimate plume concentrations. Approaches being developed to resolve these problems are discussed.     

一次光化学污染过程中O3和NOx的垂直梯度观测研究

为了研究2008年北京奥运会前期污染物浓度变化特征,对北京气象塔3层高度上的大气污染物（NO2和O3）进行加强观测,分析其变化特征。观测结果表明,由于北京奥运会前期采取了严格的空气质量控制措施,NO2浓度相对车辆限行前下降了45.3%,且随着高度递增逐渐降低;O3浓度最大值和日均值有所降低,其最大值出现时间较10年前提前了12 h,且有4 h左右处于相对平稳状态。O3浓度峰值主要是受NO2的控制,O3浓度峰值出现时间提前反映出北京大气氧化效率不断提高。对于观测期间出现光化学污染事件,利用同期气象资料和大气污染监测数据分析,发现造成这次大气污染的主要原因是气象因子：地面多处于弱高压场控制中,大气层结稳定,风力较弱（小于2 m/s）,并伴随着连续高温、强辐射和低湿。     

Transformations,Lifetimes, and Sources of NO2, HONO,and HNO3 in Indoor Environments

Recent research has demonstrated that nitrogen oxides are transformed to nitrogen acids in indoor environments, and that significant concentrations of nitrous acid are present in indoor air. The purpose of the study reported in this paper has been to investigate the sources, chemical transformations and lifetimes of nitrogen oxides and nitrogen acids under the conditions existing in buildings. An unoccupied single family residence was instrumented for monitoring of NO, NO₂, NO_y, MONO, HNO₃, CO, temperature, relative humidity, and air exchange rate. For some experiments, NO₂ and HONO were injected into the house to determine their removal rates and lifetimes. Other experiments investigated the emissions and transformations of nitrogen species from unvented natural gas appliances. We determined that HONO is formed by both direct emissions from combustion processes and reaction of NO₂ with surfaces present indoors. Equilibrium considerations influence the relative contributions of these two sources to the indoor burden of HONO. We determined that the lifetimes of trace nitrogen species varied in the order NO ~ HONO > NO₂ >HNO₃. The lifetimes with respect to reactive processes are on the order of hours for NO and HONO, about an hour for NO₂, and 30 minutes or less for HNO3. The rapid removal of NO₂ and long lifetime of HONO suggest that HONO may represent a significant fraction of the oxidized nitrogen burden in indoor air.     

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 an anomalous case of high air pollution concentration in Turin after a foehn event

A case of unusually high concentrations of some urban air pollutants (CO, NO, SO₂) in Turin (Northwestern Italy) is presented. This episode occurred during the late afternoon of 7 November 1995. This day was characterised by a strong northern foehn event in the morning, which followed the passage of a cold front. The analysis has been carried out by means of data derived from the urban and suburban air quality monitoring networks, of meteorological data (wind velocity, temperature and relative humidity) from the same network and from other networks in the region, and of the output of the numerical model LAMBO (operatively used by the Regional Meteorological Service of Emilia Romagna). The analysis of meteorological data appears to be in good correlation with the distribution of the air pollutant concentrations; in particular, the high concentrations observed in the late afternoon are due to a strong thin inversion layer near the ground, developing immediately after the sudden end of the foehn episode.