Time scales of physical and chemical processes in chemically reactive plumes

The rate of non-linear chemical reactions in a dispersing plume, such as the formation of NO₂, is discussed on the basis of various models and measurements of the oxidation rate of NO. Results of calculations with four different reactive plume models are compared with a set of plume measuremeent and discussed in terms of the ration of the time scales of physical (T_p) and chemical processes (T_c), the Damköhler number:T_p/T_c. In modelling a fast non-linear chemical reaction an interaction between physical processes of dispersion and mixing and chemical reactions can be expected. Models may differ in that they assume either chemical equilibrium (T_p/T_c⪢1) or no chemical equilibbrium (T_p/T_c⪡1).From our study it is concluded that for the first 5 km from a stack concentrations in the plume change more rapidly by dilution due to dispersion of the plume than by chemical reactions. Farther off it is the other way around and the chemistry is fast enough to achieve chemical equilibrum in the plume parcels.Conversion of NO is then inhibited by the mixing rate of the plume with its surrounding air. To incorporate the mixing rate of the plume correctly into a model, in principle the concentration distribution in a momentary plume has to be used. If a non-linear chemical reaction is modelled it is therefore important to establish the averaging times on which the dispersion parameters in the model are based. The contribution of plume meandering to dispersion, which is especially important in the daytime, can be eliminated by taking shorter averaging times. This leads to a marked improvement of modelling results. Further research is required to investigate how the contribution of fluctuations in the concentrations around the mean has to be incorporated into a model of a chemically reactive plume.     

Uncertainty in dispersion modelling and urban air quality mapping

The ADMS-urban atmospheric dispersion modelling system has been applied to review of air quality in central London in 1996/1997 and assessment of future air quality against air quality objectives in 2005. Model performance is assessed by in situ validation against monitoring data. This case study illustrates how scientific uncertainty needs to be considered when using model output in such a policy context. Model precision, carefully defined, is ±10% with bias between 0 and +12% (model over-prediction) for annual mean nitrogen dioxide and respirable particulate (PM₁₀) concentrations and for the 90th percentile of daily mean PM₁₀. As expected, the model is less accurate for the maximum and 99.8th percentile of hourly mean nitrogen dioxide concentrations and for total NO_x. We propose probabilistic mapping techniques should be used to formalise and clarify how uncertainty is translated into the definition of an Air Quality Management Area (AQMA) on a map. This also identifies the extent to which air quality objectives have been defined for which current dispersion model performance is inadequate. It is recommended that the capabilities of modelling alongside measurement need to be considered at an early stage in the formulation of future air quality management policy.     

Large-eddy simulation of a turbulent reacting plume

The results of large-eddy simulations (LES) of a chemically reacting, dispersing plume in a turbulent boundary layer are presented. The detailed simulations of the dispersion mechanisms are used to investigate the effects of turbulent fluctuations on nonlinear chemical reactions. The idealized single reaction between ozone and nitrogen oxides, NO+O₃→NO₂+O₂, is used as a representative simple, irreversible binary reaction. Effects of different reaction rates are investigated by varying the source NO concentration, while maintaining a constant ambient ozone level. The simulations demonstrate that the rate of production of NO₂ is significantly affected by the turbulent nature of the dispersing plume. The effect of incomplete turbulent mixing of the two reactants on the reaction rate can persist for long distances downstream, particularly for the high NO levels typical of power plant stacks. The LES results also show that the important measure of the turbulent fluctuations, the turbulence segregation coefficient, may be reasonably approximated by a constant value over most of the plume cross-section. This result may prove useful for simplified plume modeling, but will depend on whether the range of constant segregation coefficient covers the whole reaction region since this takes place predominantly in the plumeedges.     

Climate-driven changes in air quality over Europe by the end of the 21st century,with special reference to Portugal

Climate change alone may deeply impact air quality levels in the atmosphere because the changes in the meteorological conditions will induce changes on the transport, dispersion and transformation of air pollutants. The aim of this work was to evaluate the impact of climate change on the air quality over Europe and Portugal, using a reference year (year 1990) and a IPCC SRES A2 year (year 2100). The Hadley Centre global atmospheric circulation model (HadAM3P) was used to provide results for these two climatic scenarios, which were then used as synoptic forcing for the MM5-CHIMERE air quality modelling system. In order to assess the contribution of future climate change on O₃ and PM concentrations, no changes in regional emissions were assumed and only climate change forcing was considered. The modelling results suggest that the O₃ monthly mean levels in the atmosphere may increase almost 50 μg m^?3 across Europe in July under the IPCC SRES A2 scenario. In Portugal, this increase may reach 20 μg m^?3. The changes of PM10 monthly average values over Europe will depend on the region. The increase in PM10 concentrations during specific months could be explained by the average reduction of the boundary layer height and wind speed.     

Model calculating annual mean atmospheric dispersion factor for coastal site of nuclear power plant

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Ozone concentrations at a remote mountain site and at two regional locations in southwestern Alberta

Ozone concentrations at a remote site in the Rocky Mountains of southwestern Alberta averaged 43.4 ppb over a 2 year period and the Canadian air quality objective of an 80 ppb hourly average was exceeded 1.5% of the time. The diurnal variation in O₃ concentrations was small, 2.9 ppb, indicative of a remote location, above the nocturnal inversion and not greatly influenced by local emissions. During the period when O₃ concentrations were highest, winds were generally from the southwest, suggestive of the long range transport of anthropogenic pollutants from distant sources rather than the generation of O₃ from local emissions. In contrast, hourly O₃ concentrations at two regional air quality monitoring sites showed an average diurnal variation of 14 ppb. Only two hourly averages exceeded 80 ppb during the 2 years, and the mean O₃ concentration was 26 ppb. When these regional sites were within the urban plume from Calgary, the O₃ concentrations were depressed to a mean of 18 ppb. Ozone concentrations in downtown Calgary averaged 13 ppb. Under Alberta climatological and meteorological conditions, hourly O₃ objectives are most likely to be exceeded in remote areas, rather than in cities or in areas under the direct influence of urban emissions.     

Organic peroxy radicals: Kinetics,spectroscopy and tropospheric chemistry

The present state of knowledge of organic, or carbon-based, peroxy radicals (RO₂) is reviewed. Data on the chemical and physical properties of peroxy radicals in the gas-phase is considered, as well as the role of peroxy radicals in tropospheric chemistry and measurements of their concentrations in the atmosphere. Where appropriate, peroxy radicals are grouped together by type (alkyl, acyl, oxygen-substituted, halogen-substituted and aromatic radicals) to facilitate comparison. Data on the hydroperoxy radical (HO₂) is included where it is directly relevant to measurements on organic peroxy radicals, eg. absorption cross-sections used in measurements of RO₂ + HO₂ rate constants. The literature data is critically reviewed and recommendations for absorption cross-sections, rate constants and branching ratios are made where considered appropriate.The laboratory experimental techniques which have been used for the generation and detection of peroxy radicals and the products of their reactions are discussed. The structure, spectroscopy and thermochemistry of the radicals are examined. Although the majority of spectroscopic data concerns the u.v. spectra much used for kinetic studies, near-infrared, infrared and electron spin resonance spectra are also considered. In many cases, peroxy radical u.v. spectra are well-fitted by a Gaussian distribution function, enabling the cross-sections to be easily calculated at any wavelength.For the purpose of this review, the chemical reactions of peroxy radicals are divided into reactions with organic peroxy radicals with HO₂, with NO and NO₂, and finally with other species. Peroxy radical abstraction and addition reactions with closed-shell species are sufficiently slow to be of negligible importance at temperatures pertinent to the atmosphere and are consequently not covered. Data on both the kinetics and mechanisms of peroxy radical reactions are considered.The role of peroxy radicals as intermediates in the atmospheric degradation of volatile organic compounds and in the production of ozone in the troposphere under both low and high [NO_x] conditions is discussed. The involvement of peroxy radicals in night-time oxidation chemistry and the oxidation of halocarbons is also indicated. The techniques used for the difficult measurement of peroxy radical concentrations in the atmosphere are described, together with the results to date.Finally, some tentative suggestions as to further avenues of research are made, based on the data reviewed here and with particular reference to the solution of outstanding problems in atmospheric chemistry. Although a great deal of progress has been made in recent years, it is clear that additional work is needed in most areas covered by this review. New, sensitive and selective laboratory techniques are required for studies of peroxy radical kinetics and high level ab initio calculations would help design laser-based detection techniques. Further product studies of photooxidation systems are needed, particularly as a function of temperature. Recent work has shown that the rate constants for RO₂ + HO₂ reactions used in modelling studies may be too low; if so, these reactions will be correspondingly more important than previously believed in tropospheric oxidation. Recent kinetic studies of the potentially important reactions of methylperoxy radicals with ClO and NO₃ need to be confirmed and mechanistic work is necessary. Although substantial progress has been made towards the monitoring of peroxy radical concentrations in the atmosphere, more work is needed, both on measurements and the development of new techniques.     

Velocity oscillations and plume dispersion in a residential neighborhood during wintertime nights

Measurements of velocity and tracer plume concentrations during stable atmospheric conditions were obtained in the Boise River Valley as part of the EPA Integrated Air Cancer Project during December, 1986. Wind speed, temperature, and wind direction were measured at two levels on a 30 m tower. Spectral and autocorrelation analyses of the velocity component data clearly indicate the occurrence of wave-like oscillations in the flow and the almost complete lack of turbulent energy. The predominate wave-like motion had an oscillation period of about 1000 s. Halogenated atmospheric tracers were released from as many as four houses during the night-time drainage conditions. Hourly averaged horizontal dispersion coefficients were very large compared to the Pasquill-Gifford curves and the urban McElroy-Pooler dispersion curves. The time-averaged dispersion coefficients formed an upper bound on very short-term dispersion coefficients obtained from mobile traverses of the tracer plume with a continuous SF₆ analyzer. These results agree with the concept of a narrow instantaneous plume with a broad meander driven by the observed 1000 s oscillation. Vertical dispersion rates were slightly smaller than the Pasquill-Gifford class F curve. Results from a single tracer release from a side canyon near the neighborhood showed that drainage flow from the tributary impacted the main residential sampling site at Elm Grove Park and represented a significant fraction of the upstream air flow at Elm Grove Park. For sources with equal emission rates, a source in the tributary adds about 10% to the mean of the concentration caused by a neighborhood source.     

Simulation of dispersion in moderately complex terrain—Part C. A dispersion model for operational use

An operational dispersion model for use in areas with complex terrain is presented. The model uses mean and turbulence quantities simulated with the fluid dynamic model presented in Part A. A large number of wind and turbulence fields are simulated with the fluid dynamic model. These simulations are put into a database and can be used in the calculations of dispersion with the operational model. To get relevant meteorological data for the model a Doppler sodar and a 10 m high mast with a temperature profile and wind and wind direction at one level are used. The model calculates a trajectory for the plume centerline from the simulated wind field, and approximates the concentration field with a bi-Gaussian distribution. For convective conditions the mixing height and the surface heat flux, used as input for the model, are being determined from the sodar measurements through relations related to the temperature structure parameter C_T² and the standard deviation of the vertical velocity. The horizontal and vertical standard deviations for the plume are determined by using the simulated turbulence quantities from the dynamic model and Eulerian velocity spectra. Simulations with the model is compared with dispersion measurements performed in an area in the southern Sweden, the Vänersborg-Trollhättan region. The geographical area is characterized by topographical features on the meso-γ-scale, i.e. 2–20 km. Thus there are forested hills, a relatively flat agricultural area and an extended lake area within the model domain. The terrain height relief is typically 80 m. The simulations show, in general, good agreement with the measured data both for unstable and stable stratifications.     

Measurements of wind speed and plume rise with a rapid-scanning Lidar

A series of 30-min means of plume rise and dispersion parameters were measured at Fawley power station on Southampton Water between May and December 1989 using a rapid-scanning Lidar. Where possible, plume parameters were determined at three distances, typically 250, 750 and 1500 m, from the stack. Simultaneous measurements of temperature profiles were made using model aircraft and of wind speed and direction using a cup anemometer and wind vane at a height of 44 m on a transmission tower. By matching time series of plume heights at different distances, absolute measurements of wind speed at plume height could be made. These measurements gave a more reliable estimate of plume rise than did surface wind speeds. It was found that, for travel distances out to 1.5 km, the Briggs formula gave a robust prediction of plume heights with C₁ = 1.38±0.07 (95% confidence limits). At Fawley, the standard error in the predicted plume height at 500 m was then 21.0 m, or 19% of the 30-min mean plume rise. For plume-level winds of less than 20 m s⁻¹, analysis of the dependence of plume height on distance, wind speed and power-station load gave a virtual source height of 195.2±10.3 m (95% confidence limits). This is identical with the physical stack height of 198.1 m.     

Sodar in air pollution meteorology

Information concerning atmospheric stability and turbulence is basic in studies related to air pollution meteorology. In this context a monostatic sodar has been operating at the National Physical Laboratory, New Delhi, for many years to probe the thermal structure of the lower atmosphere in real time and space.Various observed thermal structures viz. nocturnal inversion, thermal plumes, formation and break-up of inversion, orographical mixing, multilayered structures and waves etc., are the result of the different atmospheric stabilities and turbulence conditions. These structures have been studied in the light of surface measurements of wind speed and direction for organized indexing of the structural details to infer meteorological conditions concerning Pasquill stability classifications.The height of the ground-based thermal structure has been correlated with the Richardson number, Ri, for quantitative estimation of the turbulence parameter. Estimated values of Ri have been further used to determine the cross wind dispersion coefficient, σ_y. The results obtained are realistic and can be used as input parameters for air pollution modelling.     

Evaluation of a model for hourly spatial concentration distributions

A time-dependent finite difference model in three levels combined with a puff model to account for subgrid effects close to single sources was used to calculate hour-to-hour concentration distributions. Measurements from several selected stations were used to account from time variation in background concentrations. For each hour, weight was given to observed values in areas that were not influenced by local sources.Results of concentration calculations based on hourly data on emission and dispersion are validated by measured time series of SO₂ and NO_x at five stations. A combination of hourly nephelometer readings and 12-h measurements of small particles at three stations are compared with calculated values.Hourly observed and calculated values from two periods (3 January–15 March 1988 and 18 April–24 June 1988) were used for the evaluation of the model for calculating hourly pollution concentrations in each square kilometre. The results showed that prediction of short-term average concentrations (e.g. hourly data) are usually poorly correlated with observations at the same time and location. Slight displacement errors may cause point-to-point correlation to be poor as a result of errors in input data.The pattern of NO_x concentration variation with time was reproduced well at all stations. A subgrid model taking into account the influence of nearby roads would probably improved the model for NO_x at some stations. For SO₂ and small particles, industrial sources have the dominant influence and the correspondence between observed and calculated values were improved by taking into account spatial uncertainty and an hourly variation in background concentrations.     

Statistics of concentrations due to single air pollution sources to be applied in numerical modelling of pollutant dispersion

A test of goodness of fit based on rank statistics was applied to prove the applicability of the Eggenberger-Polya discrete probability law to hourly SO₂-concentrations measured in the vicinity of single sources. With this end in view, the pollutant concentration was considered an integral quantity which may be accepted if one properly chooses the unit of measurement (in this case μg m⁻³) and if account is taken of the limited accuracy of measurements.The results of the test being satisfactory, even in the range of upper quantiles, the Eggenberger-Polya law was used in association with numerical modelling to estimate statistical parameters, e.g. quantiles, cumulative probabilities of threshold concentrations to be exceeded, and so on, in the grid points of a network covering the area of interest. This only needs accurate estimations of means and variances of the concentration series which can readily be obtained through routine air pollution dispersion modelling.     

A numerical simulation of airflows and SO2 concentration distributions in an arid south-western Valley

Three-dimensional numerical models were used to simulate wind and turbulence distributions in the Mohave Valley and plume transport from the Mohave Power Project, located at approximately 120 km south-south-east of Las Vegas, NV. The Modeled meteorological variables were input to a three-dimensional random-puff diffusion model to simulate observed tetroon trajectories and ground-level concentrations of SO₂ in the Valley. Numerical simulations indicated that hourly averaged surface concentrations could differ considerably, even when the mean and turbulence variables of the airflows were kept statistically identical. The concentration variations resulted from the differences in initial turbulence velocity and inhomogeneous distributions of airflows that each puff encountered during transport. Because the range of variations is, in general, unknown for both measurements and simulations, it is difficult to assess the representativeness of the observed and simulated values, and therefore to evaluate quantitatively the modeled concentrations against observations.     

Physico-chemical study by two aircraft of a plume from a coal-fired power plant

During the experimental field program that was conducted in October 1985 ton study the physics and chemistry of the Le Havre power plant plume, joints flights were performed with two aircraft from EDF and KEMA. The two episodes with very different meteorological conditions were investigated. The first episode was characterized by fairly constant wind speed and direction with altitude, low solar irradiation and neutral vertical dispersion conditions. The second episode was characterized by low wind speed and changing wind direction, high solar irradiation and stable vertical dispersion conditions. During the latter episode, the concentrations of emitted gases, SO₂ and NO_x remained high, even at several tens of km downwind of the stock. Increased SO₄^2- and NO₃^- concentrations were detected in the power plant plume. In addition, important photochemical activity took p-lace in the plume of a nearby industrial area. The former episode showed more significantly vertical dilution and oxidation of NO but did not reveal any contribution of the power plant plume to aerosol formation.     

GIS aided prediction of CO2 emission dispersion from geothermal electricity production

CO₂ is the dominant constituent of non-condensable gases in the steam phase of most geothermal fluids. This paper attempts to present the results of a study conducted to develop prediction modeling of CO₂ dispersion in the surrounding atmosphere from a planned 50 MWe geothermal power plant prior to its production. Dispersion models are widely used for predicting future concentrations of environmental emissions on a range of geographic scales. The dispersion type for gases and their average removal rate depends on the meteorological conditions such as wind direction, wind speed, precipitation, atmospheric stability, and surface roughness and topography. Geographic Information System (GIS) capabilities were used for quality visualization of the model outputs and presenting an accurate numerical copy of the study area. The results by the prediction model show that the natural transfer of CO₂ will be from the power plant toward east and northeast and CO₂ concentration trends after the power plant utilization will be similar to the background conditions with minor changes. This dispersion test was carried out to validate and field test the GIS aided dispersion modeling approach described in the paper and the procedure may be applicable for other studies assessing the emission dispersion of pollutants from a point source.     

Comparative study of seasonal air pollutant behavior in a Mediterranean coastal site: Castellón (Spain)

During January, July and August 1988, two experimental campaigns were carried out in the surroundings of the Castellón industrial area located on the Spanish east coast. The main objective was to study the dispersion of the power plant plume located on this site. This work also forms part of a larger program intended to compose a mosaic of atmospheric mesoscale flows related to air pollution cycles for the whole of the Iberian peninsula.In this program, air pollutants have also been considered as tracers of opportunity of the atmospheric circulations, and the study of ground-level concentration cycles has been used to provide evidence for the meso-meteorological processes. On the Castellón coast, and for most of the year, surface atmospheric dynamics are dominated by local cycles of north-west nocturnal drainage winds and east to south-south-east daytime sea-breeze flows. This regime is particularly marked during the summer, while the effect of large scale synoptic conditions is more noticeable in winter and spring.A mobile laboratory was used to collect 10 min averaged values of O₃, NO, NO₂, and SO₂. This unit was placed in the expected zone of influence of the coastal industries during the sea-breeze regime. Data obtained under summer and winter conditions have been compared and, while the temporal evolution of the concentrations of the compounds studied have similar structures, high ozone values have been detected in association with the onset of the sea-breeze during the summer.     

A computational model for the rise and dispersion of wind-blown,buoyancy-driven plumes—I. Neutrally stratified atmosphere

A multi-dimensional computational model for the rise and dispersion of a wind-blown, buoyancy-driven plume in a calm, neutrally stratified atmosphere is presented. Lagrangian numerical techniques, based on the extension of the vortex method to variable density flows, are used to solve the governing equations. The plume rise trajectory and the dispersion of its material in the crosswind plane are predicted. It is found that the computed trajectory agrees well with the two-thirds power law of a buoyancy-dominated plume, modified to include the effect of the initial plume size. The effect of small-scale atmospheric turbulence, modeled in terms of eddy viscosity, on the plume trajectory is found to be negligible. For all values of buoyancy Reynolds number, the plume cross-section exhibits a kidney-shaped pattern, as observed in laboratory and field experiments. This pattern is due to the formation of two counter-rotating vortices which develop as baroclinically generated vorticity rolls up on both sides of the plume cross-section. Results show that the plume rise can be described in terms of three distinct stages: a short acceleration stage, a long double-vortex stage, and a breakup stage. The induced velocity field and engulfment are dominated by the two large vortices. The effect of a flat terrain on the plume trajectory and dispersion is found to be very small. The equivalent radii of plumes with different initial cross-sectional aspect ratios increase at almost the same rate. A large aspect-ratio plume rises slower initially and then catches up with smaller aspect-ratio plumes in the breakup stage. The Boussinesq approximation is found to be valid if the ratio of the density perturation to the reference density is less than 0.1.     

Effect of chromium oxide as active site over TiO2-PILC for selective catalytic oxidation of NO

This study introduced TiO2-pillared clays （TiO2-PILC） as a support for the catalytic oxidation of NO and analyzed the performance of chromium oxides as the active site of the oxidation process. Cr-based catalysts were prepared by a wet impregnation method. It was found that the 10 wt.% chromium doping on the support achieved the best catalytic activity. At 350℃, the NO conversion was 61% under conditions of GHSV = 23600 hr^-l. The BET data showed that the support particles had a mesoporous structure. Hz-TPR showed that Cr（10）TiP （10 wt.% Cr doping on TiO2-PILC） clearly exhibited a smooth single peak. EPR and XPS were used to elucidate the oxidation process. During the NO ＋ O2 adsorption, the intensity of evolution of superoxide ions （O2^-） increased. The content of Cr^3＋ on the surface of the used catalyst was 40.37%, but when the used catalyst continued adsorbing NO, the Cr^3＋ increased to 50.28%. Additionally, Oα/Oβ increased markedly through the oxidation process. The NO conversion decreased when SO2 was added into the system, but when the SO2 was removed, the catalytic activity recovered almost up to the initial level. FT-IR spectra did not show a distinct characteristic peak of SO4^2-.     

A large-eddy simulation of a line source in a convective atmospheric boundary layer—II. Dynamics of a buoyant line source

We consider a large-eddy simulation of a buoyant line source in a convective boundary layer. The motion of the line source as a function of time is influenced by two contributions: internal buoyancy (plume rise) and ambient turbulence. The advantage of large-eddy modelling with respect to laboratory and atmospheric experiments is that the simulations allow us to distinguish between these two contributions. For the part due to internal buoyancy we formulate an integral model for plume rise. A new feature in this model is the fact that plume looping, which is characteristic for plume dispersion in a convective boundary layer, promotes entrainment and therefore reduces plume rise. The contribution by ambient turbulence to plume motion is modelled in terms of the standard deviation of vertical velocity fluctuations. The results of these models are consistent with our large-eddy simulations.