Sensitivity of particle deposition to changes in deposition velocity

A simple two-dimensional numerical model is used to study the sensitivity of particle deposition to changes in deposition velocity. Diurnal variations in wind speed, stability and surface resistance are considered. For the relatively small values of deposition velocity normally attributed to small particles, it was found that depletion of material exhibits a strong dependence upon the magnitude of the deposition velocity and the cycle of stabilities encountered. These results are in contrast to some other findings valid for small surface resistance values.     

Sensitivity analysis of a parameterization of the stomatal component of the DO3SE model for Quercus ilex to estimate ozone fluxes

A sensitivity analysis of a proposed parameterization of the stomatal conductance (g(s)) module of the European ozone deposition model (DO(3)SE) for Quercus ilex was performed. The performance of the model was tested against measured g(s) in the field at three sites in Spain. The best fit of the model was found for those sites, or during those periods, facing no or mild stress conditions, but a worse performance was found under severe drought or temperature stress, mostly occurring at continental sites. The best performance was obtained when both f(phen) and f(SWP) were included. A local parameterization accounting for the lower temperatures recorded in winter and the higher water shortage at the continental sites resulted in a better performance of the model. The overall results indicate that two different parameterizations of the model are needed, one for marine-influenced sites and another one for continental sites.     

Comprehensive sensitivity analysis of an SO2 deposition model for three measurement sites: Consequences for SO2 deposition fluxes

A parameterization for the dry deposition of SO₂ is evaluated by means of four statistical sensitivity studies using a sampling-based approach to sensitivity analysis. Measurements over a heathland, grassland and coniferous forest are used to identify those meteorological and vegetation-specific factors which drive the deposition component of the model (model-based studies) and which are most important in the determination of model-measurement discrepancies. Sensitivity indices and scatter plots for monthly average fluxes indicate that the dominant factors are for most months related to non-stomatal components of the deposition flux.     

Interfacial transfer velocities of ozone dry deposition over agricultural soils: experimental and theoretical analysis

A mathematical dry deposition model was developed and an experiment performed to verify that the interfacial transfer velocity (V(S)) of ozone dry deposition includes the interfacial reactive velocity (V(Sr)) and interfacial kinetic velocity (V(Sk)), as determined by measuring the ozone depletion over agricultural field soils in a dry deposition chamber. Experimental results indicate that the chemical reaction (O3 + NO --> NO2 + O2) produces the reactive velocity. Observed interfacial transfer velocities depend on nitrogen oxide emission (NO) and soil temperature (T(S)). Additionally, observed kinetic velocities of conditioned field soils increased linearly with soil temperature. Moreover, observed reactive velocities of field soils increased exponentially with soil temperature, and depend on the emission rate of nitrogen oxide. Results in this study demonstrate that interfacial transfer velocities are variable velocities for long-term transportation, that influenced factors are chemical kinetics, thermodynamics and biochemical mechanisms.     

An enhanced ozone forecasting model using air mass trajectory analysis

An enhanced ozone forecasting model using nonlinear regression and an air mass trajectory parameter has been developed and field tested. The model performed significantly better in predicting daily maximum 1-h ozone concentrations during a five-year model calibration period (1993–1997) than did a previously reported regression model. This was particularly true on the 28 “high ozone” days ([O₃]>120 ppb) during the period, for which the mean absolute error (MAE) improved from 21.7 to 12.1 ppb. On the 77 days meteorologically conducive to high ozone, the MAE improved from 12.2 to 9.1 ppb, and for all 580 calibration days the MAE improved from 9.5 to 8.35 ppb. The model was field-tested during the 1998 ozone season, and performed about as expected. Using actual meteorological data as input for the ozone predictions, the MAE for the season was 11.0 ppb. For the daily ozone forecasts, which used meteorological forecast data as input, the MAE was 13.4 ppb. The high ozone days were all anticipated by the ozone forecasters when the model was used for next day forecasts.     

Sensitivity of urban ozone formation to chlorine emission estimates

Recent evidence has demonstrated that chlorine radical chemistry can enhance tropospheric volatile organic compound oxidation and has the potential to enhance ozone formation in urban areas. In order to investigate the regional impacts of chlorine chemistry in southeastern Texas, preliminary estimates of atmospheric releases of atomic chlorine precursors from industrial point sources, cooling towers, water and wastewater treatment, swimming pools, tap water, reactions of chlorides in sea salt aerosols, and reactions of chlorinated organics were developed. To assess the potential implications of these estimated emissions on urban ozone formation, a series of photochemical modeling studies was conducted to examine the spatial and temporal sensitivity of ozone and a unique marker species for chlorine chemistry, 1-Chloro-3-methyl-3-butene-2-one (CMBO), to molecular chlorine emissions estimates. Based on current estimates of molecular chlorine emissions in southeastern Texas, chlorine chemistry has the potential to enhance ozone mixing ratios by up to 11–16 ppbv. Impacts varied temporally, with emissions from cooling towers primarily responsible for a morning enhancement in ozone mixing ratios and emissions from residential swimming pools for an afternoon enhancement. Maximum enhancement in CMBO mixing ratios ranged from 59 to 69 pptv.     

Sub-canopy deposition of ozone in a stand of cutleaf coneflower

Although there has been a great deal of research on ozone, interest in exposure of native, herbaceous species is relatively recent and it is still not clear what role the pollutant has in their ecological fitness. The ozone exposure of a plant is usually expressed in terms of the concentration above the canopy or as a time-weighted index. However, to understand the physiological effects of ozone it is necessary to quantify the ozone flux to individual leaves as they develop, which requires knowing the deposition velocity and concentration of the pollutant as a function of height throughout the plant canopy. We used a high-order closure model of sub-canopy turbulence to estimate ozone profiles in stands of cutleaf coneflower (Rudbeckia laciniata L.) located in the Great Smoky Mountains National Park, USA. The model was run for periods coinciding with a short field study, during which we measured vertical concentration profiles of ozone along with measurements of atmospheric turbulence and other meteorological and plant variables. Predictions of ozone profiles by the model are compared with observations throughout the canopy.     

Simple model for estimating dry deposition velocity of ozone and its destruction in a polluted nocturnal boundary layer

Determining the destructions of both ozone and odd oxygen, O_x, in the nocturnal boundary layer (NBL) is important to evaluate the regional ozone budget and overnight ozone accumulation. This work develops a simple method to determine the dry deposition velocity of ozone and its destruction at a polluted nocturnal boundary layer. The destruction of O_x can also be determined simultaneously. The method is based on O₃ and NO₂ profiles and their surface measurements. Linkages between the dry deposition velocities of O₃ and NO₂ and between the dry deposition loss of O_x and its chemical loss are constructed and used. Field measurements are made at an agricultural site to demonstrate the application of the model. The model estimated nocturnal O₃ dry deposition velocities from 0.13 to 0.19 cm s^?1, very close to those previously obtained for similar land types. Additionally, dry deposition and chemical reactions account for 60 and 40% of the overall nocturnal ozone loss, respectively; ozone dry deposition accounts for 50% of the overall nocturnal loss of O_x, dry deposition of NO₂ accounts for another 20%, and chemical reactions account for the remaining 30%. The proposed method enables the use of measurements made in typical ozone field studies to evaluate various nocturnal destructions of O₃ and O_x in a polluted environment.     

Dry deposition of ozone on building materials. Chamber measurements and modelling of the time-dependent deposition

Tests of the dry deposition of ozone to the surfaces of a concrete floor tile and an activated carbon cloth (ACC) sample were performed in a deposition chamber. The time-dependent deposition of ozone to the material surfaces was modelled with an adsorption, desorption, reaction model. This made it possible to find deposition velocities at equilibrium, at t=∞, from shorter time runs of 48 h. The total equilibrium deposition velocity on the concrete floor tile was found to decrease from 0.08(10) to 0.057(10) cm s⁻¹ in three consecutive runs on the same sample, and was found to be 0.137(8) cm s⁻¹ on an ACC. All at a linear airflow velocity of 0.092 cm s⁻¹, RH=50% and T=22°C. Varying the airflow in the deposition chamber, the surface deposition velocity was found to equal to the total deposition velocity for the concrete floor tile. A surface deposition velocity of 0.186(8) cm s⁻¹ was found for the ACC sample. The total real area and the reaction rate constant for the decomposition of ozone was found to be larger, and the adsorption rate constant, the desorption rate constant and the mass of ozone on the surface smaller, on the ACC sample than on the concrete floor tile.     

Modelling annual pasture dynamics: Application to stomatal ozone deposition

Modelling ozone (O₃) deposition for impact risk assessment is still poorly developed for herbaceous vegetation, particularly for Mediterranean annual pastures. High inter-annual climatic variability in the Mediterranean area makes it difficult to develop models characterizing gas exchange behaviour and air pollutant absorption suitable for risk assessment. This paper presents a new model to estimate stomatal conductance (g_s) of Trifolium subterraneum, a characteristic species of dehesa pastures. The MEDPAS (MEDiterranean PAStures) model couples 3 modules estimating soil water content (SWC), vegetation growth and g_s. The g_s module is a reparameterized version of the stomatal component of the EMEP DO₃SE O₃ deposition model. The MEDPAS model was applied to two contrasting years representing typical dry and humid springs respectively and with different O₃ exposures. The MEDPAS model reproduced realistically the g_s seasonal and inter-annual variations observed in the field. SWC was identified as the major driver of differences across years. Despite the higher O₃ exposure in the dry year, meteorological conditions favoured 2.1 times higher g_s and 56 day longer growing season in the humid year compared to the dry year. This resulted in higher ozone fluxes absorbed by T. subterraneum in the humid year. High inter-family variability was found in gas exchange rates, therefore limiting the relevance of single species O₃ deposition flux modelling for dehesa pastures. Stomatal conductance dynamics at the canopy level need to be considered for more accurate O₃ flux modelling for present and future climate scenarios in the Mediterranean area.     

The humidity dependence of ozone deposition onto a variety of building surfaces

Measurements of the dry deposition velocity of O₃ to material samples of calcareous stone, concrete and wood at varying humidity of the air, were performed in a deposition chamber. Equilibrium surface deposition velocities were found for various humidity values by fitting a model to the time-dependent deposition data. A deposition velocity-humidity model was derived giving three separate rate constants for the surface deposition velocities, i.e. on the dry surface, on the first mono-layer of adsorbed water and on additional surface water. The variation in the dry air equilibrium surface deposition velocities among the samples correlated with variations in effective areas, with larger effective areas giving higher measured deposition velocities. A minimum for the equilibrium surface deposition velocity was generally measured at an intermediate humidity close to the humidity found to correspond to one mono-layer of water molecules on the surfaces. At low air humidity the equilibrium surface deposition velocity of O₃ was found to decrease as more adsorbed water prevented direct contact of the O₃ molecules with the surface. This was partly compensated by an increase as more adsorbed water became available for reaction with O₃. At high air humidity the equilibrium surface deposition velocity was found to increase as the mass of water on the surface increased. The deposition velocity on bulk de-ionised water at RH=90% was an order of magnitude lower than on the sample surfaces.     

Modelling stomatal ozone flux and deposition to grassland communities across Europe

Regional scale modelling of both ozone deposition and the risk of ozone impacts is poorly developed for grassland communities. This paper presents new predictions of stomatal ozone flux to grasslands at five different locations in Europe, using a mechanistic model of canopy development for productive grasslands to generate time series of leaf area index and soil water potential as inputs to the stomatal component of the DO(3)SE ozone deposition model. The parameterisation of both models was based on Lolium perenne, a dominant species of productive pasture in Europe. The modelled seasonal time course of stomatal ozone flux to both the whole canopy and to upper leaves showed large differences between climatic zones, which depended on the timing of the start of the growing season, the effect of soil water potential, and the frequency of hay cuts. Values of modelled accumulated flux indices and the AOT40 index showed a five-fold difference between locations, but the locations with the highest flux differed depending on the index used; the period contributing to the accumulation of AOT40 did not always coincide with the modelled period of active ozone canopy uptake. Use of a fixed seasonal profile of leaf area index in the flux model produced very different estimates of annual accumulated total canopy and leaf ozone flux when compared with the flux model linked to a simulation of canopy growth. Regional scale model estimates of both the risks of ozone impacts and of total ozone deposition will be inaccurate unless the effects of climate and management in modifying grass canopy growth are incorporated.     

Forest responses to tropospheric ozone and global climate change: an analysis

In this paper an analysis is provided on: what we know, what we need to know, and what we need to do, to further our understanding of the relationships between tropospheric ozone (O(3)), global climate change and forest responses. The relationships between global geographic distributions of forest ecosystems and potential geographic regions of high photochemical smog by the year 2025 AD are described. While the emphasis is on the effects of tropospheric O(3) on forest ecosystems, discussion is presented to understand such effects in the context of global climate change. One particular strong point of this paper is the audit of published surface O(3) data by photochemical smog region that reveals important forest/woodland geographic regions where little or no O(3) data exist even though the potential threat to forests in those regions appears to be large. The concepts and considerations relevant to the examination of ecosystem responses as a whole, rather than simply tree stands alone are reviewed. A brief argument is provided to stimulate the modification of the concept of simple cause and effect relationships in viewing total ecosystems. Our knowledge of O(3) exposure and its effects on the energy, nutrient and hydrological flow within the ecosystem are described. Modeling strategies for such systems are reviewed. A discussion of responses of forests to potential multiple climatic changes is provided. An important concept in this paper is that changes in water exchange processes throughout the hydrological cycle can be used as early warning indicators of forest responses to O(3). Another strength of this paper is the integration of information on structural and functional processes of ecosystems and their responses to O(3). An admitted weakness of this analysis is that the information on integrated ecosystem responses is based overwhelmingly on the San Bernardino Forest ecosystem research program of the 1970s because of a lack of similar studies. In the final analysis, it is recommended that systems ecology be applied in examining the joint effects of O(3), carbon dioxide and ultraviolet-B radiation on forest ecosystems.     

Use of an indoor air quality model (IAQM) to estimate indoor ozone levels

Currently, outdoor ozone levels in many U.S. cities exceed the primary health-based national ambient air quality standard. While outdoor ozone levels are an important measure of the severity of those exceedances, people typically spend more than 80 percent of their time indoors, where ozone levels are lower. Indoor ozone levels range from 10 to 80 percent of outdoor levels, with many people receiving a substantial portion of their ozone exposure while indoors. This paper uses an indoor air quality model (IAQM) to estimate indoor ozone levels by microenvironment type (home, office, and vehicle) and configuration (windows open, windows closed, older construction, weatherized, and air conditioned). The formulation of IAQM is discussed, along with specification of model parameters for ozone. The multicompartment version of IAQM is described, with a single-compartment version used for the analyses. IAQM-calculated ozone indoor-outdoor ratios compare well with research-reported values. Results indicate that ozone peak-concentration indoor-outdoor ratios range as follows: home--0.65 (windows open), 0.36 (air conditioned), 0.23 (typical construction, windows closed), and 0.05 (energy-efficient construction, windows closed); office--0.82 (heating, ventilation and air conditioning systems supplying 100 percent outdoor air), 0.60 (typical HVAC), and 0.32 (energy-efficient HVAC); and vehicle--0.41 (85 mph), 0.33 (55 mph), and 0.21 (10 mph). Analysis results are presented to characterize IAQM's sensitivity to assumed model parameters.     

Sensitivity analysis of radionuclide migration in compacted bentonite: a mechanistic model approach

Mechanistic model calculations for the migration of Cs, Ra, Am and Pb in compacted bentonite have been carried out to evaluate sensitivities with respect to different parameter variations. A surface chemical speciation/electric double layer model is used to calculate: (i) porewater composition and radionuclide speciation in solution and at the bentonite surface, yielding the distribution of mobile and sorbed species and (ii) interaction of diffusing species with negatively charged pore walls to obtain diffusion parameters. The basic scenario considers the interaction of compacted bentonite with a fresh-type groundwater; variations include the presence of bentonite impurities and saline groundwater. It is shown that these scenarios result in significant variations of porewater composition that affect migration via three mechanisms that can partly compensate each other: (1) effects on sorption through radionuclide complexation in solution, and competition of major cations for surface sites; (2) changes in radionuclide solution speciation leading to different diffusing species under different conditions; (3) effects on diffusion through changes in the electric double layer properties of the clay pores as a function of ionic strength.     

An ozone budget for the UK: using measurements from the national ozone monitoring network; measured and modelled meteorological data,and a 'big-leaf' resistance analogy model of dry deposition

Data from the UK national air-quality monitoring network are used to calculate an annual mass budget for ozone (O3) production and loss in the UK boundary layer during 1996. Monthly losses by dry deposition are quantified from 1 km x 1 km scale maps of O(3) concentration and O(3) deposition velocities based on a big-leaf resistance analogy. The quantity of O(3) deposition varies from approximately 50 Gg-O(3) month(-1) in the winter to over 200 Gg-O(3) month(-1) in the summer when vegetation is actively absorbing O(3). The net O(3) production or loss in the UK boundary layer is found by selecting days when the UK is receiving "clean" Atlantic air from the SW to NW. In these conditions, the difference in O(3) concentration observed at Mace Head and a rural site on the east coast of the UK indicates the net O(3) production or loss within the UK boundary layer. A simple box model is then used to convert the concentration difference into a mass. The final budget shows that for most of the year the UK is a net sink for O(3) (-25 to -800 Gg-O(3) month(-1)) with production only exceeding losses in the photochemically active summer months (+45 Gg-O(3) month(-1)).     

Sensitivity of ozone to precursor emissions in urban Beijing with a Monte Carlo scheme

In order to understand the formation mechanisms of high surface ozone and identify the main contributor sources in Beijing, this study investigates the sensitivity of surface ozone to NO, NO₂ and nine types of NMVOC emissions during a photochemical smog episode. Monte Carlo sensitivity analysis scheme with fifty simulations is established based on the Nested Air Quality Prediction Model System (NAQPMS). At every simulation, each of the eleven precursor emissions is perturbed with a distinct set of perturbations. The sensitivities of ozone to emissions are identified by multiple linear regressions. The stability of sensitivity results is validated by two experiments with standard deviations of log-normal perturbations set as 30% and 50% respectively. The sensitivity results suggest that the current high surface ozone is strongly stimulated by NMVOC emissions. Among NMVOC emissions, formaldehyde, ethylene and olefins emissions present the greatest impacts on ozone. On the other hand, NOx emissions have a strong inhibitory effect on ozone formation, even after 50% NOx emission reduction. This indicates that the current ozone formation in Beijing is under NOx-saturated conditions. A transition of ozone formation is observed from NOx-saturated to NOx-limited sensitivity behavior with a 75% reduction of NOx emissions. This study gives the implication that abatement of the four NMVOC types mentioned above could be efficient on reducing the high levels of surface ozone in central urban Beijing, while inadequate abatement in NOx emissions probably induces reverse effects.     

First-order sensitivity analysis of models with time-dependent parameters: an application to PAN and ozone

A major limitation of the decoupled direct method for local sensitivity analysis (Dunker, 1984, Journal of Chemical Physics 81; 2385–2393; Gao, 1995, Ph.D. Thesis, University of Connecticut; McCroskey and McRae, 1987, Documentation for the direct decoupled sensitivity analysis method-DDM, Pittsburgh, PA) has been its restriction to the calculation of sensitivity coefficients for constant rate parameters. Realistic atmospheric simulations require that the rate parameters in chemical mechanisms, especially photolysis rate parameters and rate parameters strongly affected by temperature variations, vary diurnally during a simulation. For this reason a new conceptual framework has been devised where time-dependent rate parameters are expressed as products of time-varying profiles and time-independent multipliers. For computational convenience the nominal values of the time-independent multipliers are chosen to be unity. According to the new procedure the decoupled direct method is used to calculate the derivatives of the concentrations with respect to each time-independent multiplier. These derivatives represent the sensitivity of the concentrations to the time-varying profiles of the time-dependent rate parameters. Local sensitivity coefficients for O₃ and PAN were calculated for a moderately polluted scenario that was free of clouds and at a constant temperature using the Regional Atmospheric Chemistry Mechanism (RACM) (Stockwell et al., 1997, Journal of Geophysical Research 102, 25,847–25,879). Calculations were compared for simulations with constant as well as diurnally changing photolysis rate coefficients. The results show that sensitivity coefficients calculated using constant, average, rate parameter values may be significantly different from sensitivity coefficients calculated using time-varying rate parameters and therefore the relative importance of the mechanism's reactions may be different for the two calculations. The greatest differences in sensitivity coefficients were found for reactions with rates that have strong diurnal variations, such as photolysis, HO and NO₃ reactions. It was further found that diurnally varying reactions have cumulative effects on sensitivity coefficients during the simulation of an episode that are not present when constant rate parameters are used. These results have implications, not only for sensitivity analysis and modelling, but also for the use of measurements to validate chemical models.