A note on subgrid-scale processes in photochemical modelling

The effects of including a parameterization of subgrid-scale dispersion and chemical processes in the Eulerian-Lagrangian transport model of Hess are investigated. A case chosen to maximize the subgrid-scale effects is studied, and it is found that the predicted change in maximum O₃ when subgrid-scale processes are included is small (∼5%) compared with predictions based on direct injection of point emissions. It is also found for this model that the parameterization of subgrid-scale processes is not necessary to provide numerical stability in calculating the chemical kinetics.     

Comparison of a new Eulerian model with a modified Lagrangian approach for particle distribution and deposition indoors

Understanding of aerosol dispersion characteristics has many scientific and engineering applications. It is recognized that Eulerian or Lagrangian approach has its own merits and limitations. A new Eulerian model has been developed and it adopts a simplified drift–flux methodology in which external forces can be incorporated straightforwardly. A new near-wall treatment is applied to take into account the anisotropic turbulence for the modified Lagrangian model. In the present work, we present and compare both Eulerian and Lagrangian models to simulate particle dispersion in a small chamber. Results reveal that the standard k–ε Lagrangian model over-predicts particle deposition compared to the present turbulence-corrected Lagrangian approach. Prediction by the Eulerian model agrees well with the modified Lagrangian model.     

Fully coupled “online” chemistry within the WRF model

A fully coupled “online” Weather Research and Forecasting/Chemistry (WRF/Chem) model has been developed. The air quality component of the model is fully consistent with the meteorological component; both components use the same transport scheme (mass and scalar preserving), the same grid (horizontal and vertical components), and the same physics schemes for subgrid-scale transport. The components also use the same timestep, hence no temporal interpolation is needed. The chemistry package consists of dry deposition (“flux-resistance” method), biogenic emission as in [Simpson et al., 1995. Journal of Geophysical Research 100D, 22875–22890; Guenther et al., 1994. Atmospheric Environment 28, 1197–1210], the chemical mechanism from RADM2, a complex photolysis scheme (Madronich scheme coupled with hydrometeors), and a state of the art aerosol module (MADE/SORGAM aerosol parameterization).The WRF/Chem model is statistically evaluated and compared to MM5/Chem and to detailed photochemical data collected during the summer 2002 NEAQS field study. It is shown that the WRF/Chem model is statistically better skilled in forecasting O₃ than MM5/Chem, with no appreciable differences between models in terms of bias with the observations. Furthermore, the WRF/Chem model consistently exhibits better skill at forecasting the O₃ precursors CO and NO_y at all of the surface sites. However, the WRF/Chem model biases of these precursors and of other gas-phase species are persistently higher than for MM5/Chem, and are most often biased high compared to observations. Finally, we show that the impact of other basic model assumptions on these same statistics can be much larger than the differences caused by model differences. An example showing the sensitivity of various statistical measures with respect to the treatment of biogenic volatile organic compounds emissions illustrates this impact.     

Numerical modeling of dry deposition coupled to 22 photochemical reactions

Three Eulerian models for the dry deposition of photochemically reactive species were formulated and evaluated: a K-theory model with independent transport and deposition of each species, a K-theory model coupled with 22 gas-phase reactions, and a second-order flux-budget model coupled with 22 reactions. Operator splitting was used to separately solve the reaction and dispersion terms in the models including photochemistry. In an evaluation of numerical method performance, the Adams–Moulton method with a pseudo-steady-state approximation for the free radicals was found to be consistent with, but more computationally efficient than Gear’s method for the solution of the reaction terms. The sensitivity of profiles of vertical concentration and flux to the Eulerian model formulation varied according to the species’ Damköhler number. Although a K-theory model is adequate for weakly depositing species with Damköhler numbers <10^-3, a second-order flux-budget model is required for species with Damköhler numbers that exceed unity, such as nitrogen oxides, free radicals, and those sensitive to net flux production by chemical reactions. Selection of an appropriate model formulation for the entire system depended on the most reactive species. Simple K-theory models may not accurately predict dry deposition fluxes in the urban surface layer.     

The Danish eulerian hemispheric model — a three-dimensional air pollution model used for the arctic

A three-dimensional Eulerian hemispheric air pollution model, the Danish Eulerian Hemispheric Model (DEHM), is in development at the National Environmental Research Institute (NERI). The model has been used to study long-range transport of air pollution in the Northern Hemisphere. The present version of the model includes long-range transport of sulphur dioxide (SO₂) and particulate sulphate (SC₄²⁻. The chemistry in the model is described by a simple linear oxidation of SO₂ to SO₄²⁻, and the wet deposition of SO₂ and SO₄⁻ is estimated based on the amount of precipitation, which is calculated from the contents of liquid cloud water (see Christensen, Air Pollution Modelling and its Applicatioons, Vol. X, pp. 119–127, Vol. XI, pp. 249–256, Plenum press, New York; 1995, Ph.D. thesis, National Environmental Research Institute, Denmark). The model has been used to study the air pollution in the Arctic. Results from yr simulation with an analysis of the results is presented: the model results are verified by comparisons, to measurements not only from the Arctic region but also from Europe and Canada. Some examples of episodes in the Arctic including analysis of the meteorological conditions during the episodes are presented. Finally, the model has been used to estimate the contribution from the different source regions on the northern hemisphere to the Arctic sulphur pollution.     

Modeling Atmospheric Mercury Deposition in the Vicinity of Power Plants

Abstract

Two mathematical models of the atmospheric fate and transport of mercury (Hg), an Eulerian grid–based model and a Gaussian plume model, are used to calculate the atmospheric deposition of Hg in the vicinity (i.e., within 50 km) of five coal–fired power plants. The former is applied using two different horizontal resolutions: coarse (84 km) and fine (16.7 km). More than 96% of the power plant Hg emissions are calculated with the plume model to be transported beyond 50 km from the plants. The grid–based model predicts a lower fraction to be transported beyond 50 km: >91% with a coarse resolution and >95% with a fine resolution. The contribution of the power plant emissions to total Hg deposition within a radius of 50 km from the plants is calculated to be <8% with the plume model, <14% with the Eulerian model with a coarse resolution, and <10% with the Eulerian model with a fine resolution. The Eulerian grid–based model predicts greater local impacts than the plume model because of artificially enhanced vertical dispersion; the former predicts about twice as much Hg deposition as the latter when the area considered is commensurate with the resolution of the grid–based model. If one compares the local impacts for an area that is significantly less than the grid–based model resolution, then the grid–based model may predict lower local deposition than the plume model, because two compensating errors affect the results obtained with the grid–based model: initial dilution of the power plant emissions within one or more grid cells and enhanced vertical mixing to the ground.     

Non-linear response of wet deposition to emissions reduction: A model study

An Eulerian atmospheric model with complex chemistry (Acidic Deposition and Oxidant Model) and a Lagrangian model with linear chemistry (Ontario Ministry of the Environment Trajectory Model) were used to simulate the wet SO₄²⁻ deposition pattern over eastern North America for 16 days during April 1981.The two model results agree reasonably well with each other when the 16 day average values are compared. They also show reasonable agreement with observed data. Having established the ability of the models to predict deposition patterns for 1981 emissions, reduction scenarios with 50% SO_x and 50% SO_x and NO_x of the 1981 emissions were studied through the Eulerian model. Near the heavy emissions area, the reduction in SO₄²⁻ wet deposition is only about 30–40%. In this respect the linear Lagrangian model departs significantly from the Eulerian model. This non-linearity in response is attributed to the role of oxidants in controlling the conversion of SO₂ to SO₄²⁻.     

Removal of sulphur dioxide in a two-dimensional rain system based on a scale analysis of the conservation equations

Since rain systems show a wide variation in structure in both time and space, it is virtually impossible to model in detail the behaviour of sulphur passing through a rain system. Instead, an attempt has been made to determine the scale of the major processes going on in a frontal rain system based on the conservation equations for cloudwater, rainwater, SO₂ in air, sulphate in cloud and sulphate in rainwater. When this procedure is followed it is found that cloud and rainwater amounts are determined largely as a dynamic balance between cloudwater condensation and accretion of cloud drops by rain. The removal of SO₂ in rain is mainly determined by the oxidation of SO₂ in cloud, enhanced by oxidation in rain. In the case when oxidation of SO₂ by O₃ is the primary oxidation pathway a simple formula is derived for the fractional removal efficiency, which shows which parameters are of greatest importance and has potential use in the current generation of long-range transport models. This formula shows that the removal efficiency is a strongly non-linear function of sulphur dioxide concentration. At regional average SO₂ concentrations removal is efficient, but decreases rapidly at higher SO₂ concentrations.     

Measurement of Ozone Concentration

A method based on hourly NWS cloud amount reports is presented for developing a simple model to account for cloud cover in the determination of the nitrogen dioxide photolysis rate constant, k ₁ The model is parameterized and verified with direct UV radiometer and k ₁ measurements (vs. time of day) collected by Sickles, et al. ¹ at Research Triangle Park. Application of our model to variable cloud condition situations indicates that significant improvement in k ₁ prediction is obtained by including the influence of cloud cover. Comparison of our model with the radiative transfer calculations of Peterson⁷ indicates that the particular parameterization of k ₁ given here is most representative of average albedo and relatively heavy aerosol loading conditions. Comparison of ozone predictions using hourly averaged k ₁ and instantaneous k ₁ under conditions of varying cloud cover suggest that the errors resulting from averaging k ₁ are largest when variations in solar zenith angle are significant over the hour.     

Stochastic simulation of meteorological variability for long-range atmospheric transport—II. Long-term statistical models

Methods are developed for simulating meteorological inputs for statistical atmospheric transport models. Stochastic models are presented for the annual mean wind vector, the horizontal diffusion coefficient, the fraction of time it is raining, and the quantity of precipitation. The models are derived by aggregating the statistical models for short-term meteorological processes given in the companion paper of Small and Samson (Atmospheric Environment, 1989, 23, 2813–2824). Normal distributions are used for each variable. The normal distribution is derived directly for the mean wind vector based on the normality of short-term winds, and serves as an acceptable approximation for the other variables given their low interannual coefficient of variation. Correlation between variables is considered, including correlation between winds and precipitation, between the fraction of time it is raining and the total quantity of precipitation at a site, and between the annual precipitation quantity at multiple sites. Development and confirmation of the interannual distributions is supported by long-term meteorological data, including a nine-year backward trajectory record computed for a site in western Pennsylvania. Application of the method is demonstrated with a statistical atmospheric LRT model used to predict distributions of annual precipitation sulfates in eastern North America. Predicted interannual coefficients of variation of wet SO₄²⁻ concentrations range from about 10 to 15 per cent, similar to the level of interannual variation inferred from long-term data sets.     

Mesoscale modeling of wintertime particulate matter episodes in eastern Washington, USA

The Spokane, Washington area is classified as a non-attainment area for the 24-h PM₁₀ standard due to a history of high particulate matter concentrations. A Eulerian regional air quality model (CALMET/CALGRID) has been used to characterize the emission, transport and dispersion of PM₁₀ and PM_2.5 in Spokane. Observations from a residential site (Rockwood, RW) and an industrial site (Crown Zellerbach, CZ), spanning July 1994–August 1996 were used to evaluate the current emission inventory. Two major tasks were devised to conduct the objectives of this investigation. First, a simple and efficient urban dispersion model (WYNDValley) was used to simulate important episodes characterized by the highest PM₁₀ and PM_2.5 concentrations. The selected episodes included four days with wet conditions for which no roads would have been emitting and seven days with dry conditions for which roads would emit. In the second step, a single road-emitting event was selected from the previous predicted results for further analysis using the Eulerian regional air quality model to examine the emission inventory. The urban and regional models predicted the observed concentration distributions reasonably well for the source emissions inventoried in Spokane. The mass concentrations of PM₁₀ were well predicted for the roads emitting case examined by both models indicating that the emission inventory based primarily upon area sources including roads is reasonably well characterized, at least at the RW site. The area sources around CZ are less well characterized, so that the PM₁₀ concentrations are underpredicted at CZ. The models appear unable to reach an equilibrium mass balance status at the beginning of the simulation, and the urban model seems unable to properly resolve the nocturnal boundary layer.     

Modeling the surface–atmosphere exchange of ammonia

New parameterizations for surface–atmosphere exchange of ammonia are presented for application in atmospheric transport models and compared with parameterizations of the literature. The new parameterizations are based on a combination of the results of three years of ammonia flux measurements over a grassland canopy (dominated by Lolium perenne and Poa trivialis) near Wageningen, the Netherlands and existing parameterizations from literature. First, a model for the surface–atmosphere exchange of ammonia that includes the concentration at the external leaf surface is derived and validated. Second, a parameterization for the stomatal compensation point (expressed as Γ_s, the ratio of [NH₄⁺]/[H⁺] in the leaf apoplast) that accounts for the observed seasonal variation is derived from the measurements. The new, temperature-dependent Γ_s describes the observed seasonal behavior very well. It is noted, however, that senescence of plants and field management practices will also influence the seasonal variation of Γ_s on a shorter timescale. Finally, a relation that links Γ_s to the atmospheric pollution level of the location through the ‘long-term’ NH₃ concentration in the air is proposed.     

Validation of the operational emergency response model at the Swedish Meteorological and Hydrological Institute using data from etex and the chernobyl accident

The Eulerian atmospheric tracer transport model MATCH (Multiscale Atmospheric Transport and Chemistry model) has been extended with a Lagrangian particle model treating the initial dispersion of pollutants from point sources. The model has been implemented at the Swedish Meteorological and Hydrological Institute in an emergency response system for nuclear accidents and can be activated on short notice to provide forecast concentration and deposition fields.The model has been used to simulate the transport of the inert tracer released during the ETEX experiment and the transport and deposition of ¹³⁷Cs from the Chernobyl accident. Visual inspection of the results as well as statistical analysis shows that the extent, time of arrival and duration of the tracer cloud, is in good agreement with the observations for both cases, with a tendency towards over-prediction for the first ETEX release. For the Chernobyl case the simulated deposition pattern over Scandinavia and over Europe as a whole agrees with observations when observed precipitation is used in the simulation. When model calculated precipitation is used, the quality of the simulation is reduced significantly and the model fails to predict major features of the observed deposition field.     

An investigation of the formation of ambient NH4NO3 aerosol

The aerosol equilibrium formulation of Stelson and Seinfeld (1982a, b, Atmospheric Environment16, 983–992, 993–1000) is incorporated into the STEM-II transport/chemistry model and is evaluated against NH₃, HNO₃ and aerosol NH₄⁺ and NO₃⁻ measured at Nagano Prefecture, Japan on 29 and 30 July 1983. These results indicate that this modeling approach is useful in analyzing field data.     

Model simulations of the atmospheric trace metals concentrations and depositions over the Baltic Sea

The results of application of two nested Eulerian atmospheric transport models for investigation of airborne heavy metal pollution are presented. The distribution and deposition over Europe and Baltic Sea region were simulated for Pb, Cd and Zn for 2 two-months periods: June–July 1997 and February–March 1998. The European-wide calculations were made with the ADOM model from the GKSS Research Centre, and the Baltic regional calculations were made with the HILATAR model from the Finnish Meteorological Institute. The one-way 3-D nesting was used: hourly concentrations from the ADOM model were used by the HILATAR as vertically resolved boundary conditions. Input data for both models were taken from the weather forecast model HIRLAM and UBA/TNO emission inventory. This allows interpreting of some diversity in the calculation results in terms of different internal parameterization and spatial resolution of the models. Simulation results were compared with high-resolution atmospheric measurements carried out at four stations in the southern part of the Baltic Sea for the same period. Manifesting quite good agreement with observations, the models missed several high deposition events of Cd observed at coastal station Hel. Study of this phenomenon enabled to build a 2-D probability function for potential location of the unknown Cd source.     

Models for gas/particle partitioning,transformation and air/water surface exchange of PCBs and PCDD/Fs in CMAQ

We have added the capability to simulate polychlorinated biphenyls (PCBs) and polychlorinated dibenzo [p] dioxins and polychlorinated dibenzo-furans (PCDD/Fs) to the Community Multiscale Air Quality (CMAQ) modeling system, thus taking advantage of the latter's capability to simulate atmospheric advection, diffusion, gas-phase chemistry, cloud/precipitation, and aerosol processes. The modifications reported here include the addition to the CMAQ system of two gas/particle partitioning models options: the Junge–Pankow adsorption model and the K_OA absorption model, as well as chemical transformations and atmosphere/water surface exchange processes for these semi-volatile organics. Simulations for the purpose of model testing and validation were conducted for the years 2000 and 2002 on a domain covering most of North America. Both partitioning models give reasonable results when compared with available measurements. The model predictions of deposition and air concentrations also agree well with measurements. The modeling results also indicate that the long-range transport is important and anthropogenic emissions of PCBs and PCDD/Fs are dominant although surface exchange of PCBs may be important for some clean locations.     

The effect of precipitation on the vertical profiles of atmospheric ammonia: A modeling investigation

This paper describes theoretical calculations of atmospheric ammonia profiles during precipitation events. The PLUVIUS reactive storm model (Hales, 1982, Atmospheric Environment16,1775–1783) was used in a simplified form relevant to this specific system. Calculated NH₃ profiles for dry atmospheres were consistent with distributions previously reported in the literature. NH₃ profiles in the gas and cloud phases, following a simulated convective storm, showed large variations with height. These variations are strongly dependent on storm duration. In some cases, NH₃ gas concentrations were depleted by more than 50% by the precipitation scavenging process. Modeled NH₃ gas profiles regenerate slowly with time after storm termination.     

Numerical simulation of scalar dispersion downstream of a square obstacle using gradient-transport type models

We present a numerical study of scalar transport released from a line source downstream of a square obstacle to investigate the capabilities and limitations of gradient-transport modeling in predicting atmospheric dispersion. The standard k–? and k–ω models and a Reynolds Stress Transport closure are employed and compared to predict the time-averaged turbulent flow field, while a standard gradient–diffusion model is initially adopted to relate the scalar flux to mean gradients of the concentration field. The analysis of two algebraic closures for turbulent scalar fluxes based on the generalized-gradient–diffusion hypothesis and its quadratic extension is also presented. In spite of the rather simple flow setup, where both the flow and the scalar fields can be assumed homogeneous in the spanwise direction, the analysis clarifies several critical issues concerning gradient-transport type models. We established the dominant role of predicted turbulent kinetic energy on scalar dispersion when a scalar diffusivity is employed, irrespectively of the Reynolds stress closure adopted for the averaged momentum equation. Moreover, the standard gradient–diffusion hypothesis failed to predict the streamwise component of the scalar flux, which is characterized by a counter-gradient-transport mechanism. Although the resulting contribution in the averaged scalar transport equation is small in the present flow configuration, this limitation can become severe for strongly inhomogeneous flows in the presence of point sources, where the spread of the scalar plume is essentially three-dimensional. The predictive capabilities of gradient-transport type modeling are found clearly improved using algebraic closures, which appear to represent a promising tool for predicting atmospheric dispersion in complex flows when unsteady transport mechanisms are not dominant.