Sensitivity of ozone concentrations to diurnal variations of surface emissions in Mexico City: A WRF/Chem modeling study

Sensitivity of ozone (O₃) concentrations in the Mexico City area to diurnal variations of surface air pollutant emissions is investigated using the WRF/Chem model. Our analysis shows that diurnal variations of nitrogen oxides (NO_x = NO + NO₂) and volatile organic compound (VOC) emissions play an important role in controlling the O₃ concentrations in the Mexico City area. The contributions of NO_x and VOC emissions to daytime O₃ concentrations are very sensitive to the morning emissions of NO_x and VOCs. Increase in morning NO_x emissions leads to decrease in daytime O₃ concentrations as well as the afternoon O₃ maximum, while increase in morning VOC emissions tends to increase in O₃ concentrations in late morning and early afternoon, indicating that O₃ production in Mexico City is under VOC-limited regime. It is also found that the nighttime O₃ is independent of VOCs, but is sensitive to NO_x. The emissions of VOCs during other periods (early morning, evening, and night) have only small impacts on O₃ concentrations, while the emissions of NO_x have important impacts on O₃ concentrations in the evening and the early morning.This study suggests that shifting emission pattern, while keeping the total emissions unchanged, has important impacts on air quality. For example, delaying the morning emission peak from 8 am to 10 am significantly reduced the morning peaks of NO_x and VOCs, as well as the afternoon O₃ maxima. It suggests that without reduction of total emission, the daytime O₃ concentrations can be significantly reduced by changing the diurnal variations of the emissions of O₃ precursors.     

The sensitivity of the CHIMERE model to emissions reduction scenarios on air quality in Northern Italy

The sensitivity of the CHIMERE model to emission reduction scenarios on particulate matter PM2.5 and ozone (O₃) in Northern Italy is studied. The emissions of NO_x, PM2.5 SO₂, VOC or NH₃ were reduced by 50% for different source sectors for the Lombardy region, together with 5 additional scenarios to estimate the effect of local measures on improving the air quality for the Po valley area. Firstly, we evaluate the model performance by comparing calculated surface aerosol concentrations for the standard case (no emission reductions) with observations for January and June 2005. Calculated monthly mean PM10 concentrations are in general underestimated. For June, modelled PM10 concentrations slightly overestimate the measurements. Calculated monthly mean SO₄, NO₃^?, NH₄⁺ concentrations are in good agreement with the observations for January and June. Secondly, the model sensitivity of emission reduction scenarios on PM2.5 and O₃ calculated concentrations for the Po valley area is evaluated. The most effective scenarios to abate PM2.5 concentration are based on the SNAP2 (non-industrial combustion plants) and SNAP7 (road traffic) sectors, for which the NO_x and PM2.5 emissions are reduced by 50%. The number of days that the 2015 PM2.5 limit value of 25 μg m^?3 in Milan is exceeded by reducing primary PM2.5 and NO_x emissions for SNAP2 and 7 by 50%, does not change in January when compared to the standard case for the Milan area. It appears that 40% of the PM2.5 concentration in the greater Milan area is caused by the emissions surrounding the Lombardy region and from the model boundary conditions.This study also showed that a more effective pollutant reduction (emissions) per ton of pollutant reduced (concentrations) for the greater Milan area is obtained by reducing the primary PM2.5 emissions for SNAP7 by 50%. The most effective scenario on PM2.5 decrease for which precursor emissions are reduced is achieved by reducing SO₂ emissions by 50% for SNAP7.Our study showed that during summer time, the largest reductions in O₃ concentrations are achieved for SNAP7 emission reductions, when volatile organic compounds (VOCs) are reduced by 50%.     

Precursor reductions and ground-level ozone in the Continental United States

Numerous papers analyze ground-level ozone (O₃) trends since the 1980s, but few have linked O₃ trends with observed changes in nitrogen oxide (NO_x) and volatile organic compound (VOC) emissions and ambient concentrations. This analysis of emissions and ambient measurements examines this linkage across the United States on multiple spatial scales from continental to urban. O₃ concentrations follow the general decreases in both NO_x and VOC emissions and ambient concentrations of precursors (nitrogen dioxide, NO₂; nonmethane organic compounds, NMOCs). Annual fourth-highest daily peak 8-hr average ozone and annual average or 98th percentile daily maximum hourly NO₂ concentrations show a statistically significant (p < 0.05) linear fit whose slope is less than 1:1 and intercept is in the 30 to >50 ppbv range. This empirical relationship is consistent with current understanding of O₃ photochemistry. The linear O₃–NO₂ relationships found from our multispatial scale analysis can be used to extrapolate the rate of change of O₃ with projected NO_x emission reductions, which suggests that future declines in annual fourth-highest daily average 8-hr maximum O₃ concentrations are unlikely to reach 65 ppbv or lower everywhere in the next decade. Measurements do not indicate increased annual reduction rates in (high) O₃ concentrations beyond the multidecadal precursor proportionality, since aggressive measures for NO_x and VOC reduction are in place and have not produced an accelerated O₃ reduction rate beyond that prior to the mid-2000s. Empirically estimated changes in O₃ with emissions suggest that O₃ is less sensitive to precursor reductions than is found by the CAMx (v. 6.1) photochemical model. Options for increasing the rate of O₃ change are limited by photochemical factors, including the increase in NO_x sensitivity with time (NMOC/NO_x ratio increase), increase in O₃ production efficiency at lower NO_x concentrations (higher O₃/NO_y ratio), and the presence of natural NO_x and NMOC precursors and background O₃.

Implications:?This analysis demonstrates empirical relations between O₃ and precursors based on long term trends in U.S. locations. The results indicate that ground-level O₃ concentrations have responded predictably to reductions in VOC and NO_x since the 1980s. The analysis reveals linear relations between the highest O₃ and NO₂ concentrations. Extrapolation of the historic trends to the future with expected continued precursor reductions suggest that achieving the 2014 proposed reduction in the U.S. National Ambient Air Quality Standard to a level between 65 and 70 ppbv is unlikely within the next decade. Comparison of measurements with national results from a regulatory photochemical model, CAMx, v. 6.1, suggests that model predictions are more sensitive to emissions changes than the observations would support.     

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.     

An Environmental Decision-Making Tool for Evaluating Ground-Level Ozone-Related Health Effects

Abstract

A computer model called the Ozone Risk Assessment Model (ORAM) was developed to evaluate the health effects caused by ground-level ozone (O₃) exposure. ORAM was coupled with the U.S. Environmental Protection Agency’s (EPA) Third-Generation Community Multiscale Air Quality model (Models-3/CMAQ), the state-of-the-art air quality model that predicts O₃ concentration and allows the examination of various scenarios in which emission rates of O₃ precursors (basically, oxides of nitrogen [NO_x] and volatile organic compounds) are varied. The principal analyses in ORAM are exposure model performance evaluation, health-effects calculations (expected number of respiratory hospital admissions), economic valuation, and sensitivity and uncertainty analysis through a Monte Carlo simulation. As a demonstration of the system, ORAM was applied to the eastern Tennessee region, and the entire O₃ season was simulated for a base case (typical emissions) and three different emission scenarios. The results indicated that a synergism occurs when reductions in NO_x emissions from mobile and point sources were applied simultaneously. A 12.9% reduction in asthma hospital admissions is expected when both mobile and point source NO_x emissions are reduced (50 and 70%, respectively) versus a 5.8% reduction caused by mobile source and a 3.5% reduction caused by point sources when these emission sources are reduced individually.     

Modelling NOx from lightning and its impact on global chemical fields

We have used a three-dimensional off-line chemical transport model (CTM) to assess the impact of lightning emissions in the free troposphere both on NO_x itself and on other chemical species such as O₃ and OH. We have investigated these effects using two lightning emission scenarios. In the first, lightning emissions are coupled in space and time to the convective cloud top height calculated every 6 h by the CTM's moist convection scheme. In the second, lightning emissions are calculated as a constant, monthly mean field. The model's performance against observed profiles of NO_x and O₃ in the Atlantic and Pacific ocean improves significantly when lightning emissions are included. With the inclusion of these emissions, the CTM produces a significant increase in the NO_x concentrations in the upper troposphere, where the NO_x lifetime is long, and a smaller increase in the lower free troposphere, where the surface NO_x sources dominate. These changes cause a significant increase in the O₃ production in the upper troposphere and hence higher calculated O₃ there. The model indicates that lightning emissions cause local increases of over 50 parts per 10¹² by volume (pptv) in NO_x, 200 pptv in HNO₃ and 20 parts per 10⁹ by volume (ppbv) (>40%) in O₃. In addition, a smaller increase of O₃ in the lower troposphere occurs due to an increase in the downward transport of O₃. The O₃ change is accompanied by an increase in OH which is more pronounced in the upper troposphere with a corresponding reduction in CO. The method of emission employed in the model does not appear to have a significant effect globally. In the upper troposphere (above about 300 hPa) NO_x concentrations are generally lower with monthly mean emissions, because of the de-coupling of emissions from the model's convection scheme, which vents NO_x aloft more efficiently in the coupled scheme. Below the local convective outflow altitude, NO_x concentrations are larger when using the monthly mean emissions than when coupled to the convection scheme, because the more dilute emissions, and nighttime emissions, lead to a slower NO_x destruction rate. Only minor changes are predicted in the monthly average fields of O₃ if we emit lightning as a monthly constant field. However, the method of emission becomes important when we make a direct comparison of model results with time varying data. These differences should be taken into account when a direct comparison of O₃ with measurements collected at particular times and locations is attempted.     

Modeling an air pollution episode in northwestern United States: Identifying the effect of nitrogen oxide and volatile organic compound emission changes on air pollutants formation using direct sensitivity analysis

Air quality impacts of volatile organic compound (VOC) and nitrogen oxide (NO_x) emissions from major sources over the northwestern United States are simulated. The comprehensive nested modeling system comprises three models: Community Multiscale Air Quality (CMAQ), Weather Research and Forecasting (WRF), and Sparse Matrix Operator Kernel Emissions (SMOKE). In addition, the decoupled direct method in three dimensions (DDM-3D) is used to determine the sensitivities of pollutant concentrations to changes in precursor emissions during a severe smog episode in July of 2006. The average simulated 8-hr daily maximum O₃ concentration is 48.9 ppb, with 1-hr O₃ maxima up to 106 ppb (40 km southeast of Seattle). The average simulated PM_2.5 (particulate matter with an aerodynamic diameter <2.5 μm) concentration at the measurement sites is 9.06 μg m^?3, which is in good agreement with the observed concentration (8.06 μg m^?3). In urban areas (i.e., Seattle, Vancouver, etc.), the model predicts that, on average, a reduction of NO_x emissions is simulated to lead to an increase in average 8-hr daily maximum O₃ concentrations, and will be most prominent in Seattle (where the greatest sensitivity is??0.2 ppb per % change of mobile sources). On the other hand, decreasing NO_x emissions is simulated to decrease the 8-hr maximum O₃ concentrations in remote and forested areas. Decreased NO_x emissions are simulated to slightly increase PM_2.5 in major urban areas. In urban areas, a decrease in VOC emissions will result in a decrease of 8-hr maximum O₃ concentrations. The impact of decreased VOC emissions from biogenic, mobile, nonroad, and area sources on average 8-hr daily maximum O₃ concentrations is up to 0.05 ppb decrease per % of emission change, each. Decreased emissions of VOCs decrease average PM_2.5 concentrations in the entire modeling domain. In major cities, PM_2.5 concentrations are more sensitive to emissions of VOCs from biogenic sources than other sources of VOCs. These results can be used to interpret the effectiveness of VOC or NO_x controls over pollutant concentrations, especially for localities that may exceed National Ambient Air Quality Standards (NAAQS).

Implications: The effect of NO_x and VOC controls on ozone and PM_2.5 concentrations in the northwestern United States is examined using the decoupled direct method in three dimensions (DDM-3D) in a state-of-the-art three-dimensional chemical transport model (CMAQ). NO_x controls are predicted to increase PM_2.5 and ozone in major urban areas and decrease ozone in more remote and forested areas. VOC reductions are helpful in reducing ozone and PM_2.5 concentrations in urban areas. Biogenic VOC sources have the largest impact on O₃ and PM_2.5 concentrations.     

Effects of uncertainty in the reaction of the hydroxyl radical with nitrogen dioxide on model-simulated ozone control strategies

We evaluated the effect of a 20% reduction in the rate constant of the reaction of the hydroxyl radical with nitrogen dioxide to produce nitric acid (OH+NO₂→HNO₃) on model predictions of ozone mixing ratios ([O₃]) and the effectiveness of reductions in emissions of volatile organic compounds (VOC) and nitrogen oxides (NO_x) for reducing [O₃]. By comparing a model simulation with the new rate constant to a base case scenario, we found that the [O₃] increase was between 2 and 6% for typical rural conditions and between 6 and 16% for typical urban conditions. The increases in [O₃] were less than proportional to the reduction in the OH+NO₂ rate constant because of negative feedbacks in the photochemical mechanism. Next, we used two different approaches to evaluate how the new OH+NO₂ rate constant changed the effectiveness of reductions in emissions of VOC and NO_x: first, we evaluated the effect on [O₃] sensitivity to small changes in emissions of VOC (d[O₃]/dE_VOC) and NO_x (d[O₃]/dE_NOx); and secondly, we used the empirical kinetic modeling approach to evaluate the effect on the level of emissions reduction necessary to reduce [O₃] to a specified level. Both methods showed that reducing the OH+NO₂ rate constant caused control strategies for VOC to become less effective relative to NO_x control strategies. We found, however, that d[O₃]/dE_VOC and d[O₃]/dE_NOx did not quantitatively predict the magnitude of the change in the control strategy because the [O₃] response was nonlinear with respect to the size of the emissions reduction. We conclude that model sensitivity analyses calculated using small emissions changes do not accurately characterize the effect of uncertainty in model inputs (in this case, the OH+NO₂ rate constant) on O₃ attainment strategies. Instead, the effects of changes in model inputs should be studied using large changes in precursor emissions to approximate realistic attainment scenarios.     

Control of Ozone Precursors in a Complex Industrial Terrain by Using Multiscale-Nested Air Quality Models with Fine Spatial Resolution (1 km2)

Abstract

The location of the northeastern Iberian Peninsula (NEIP) in the northwestern Mediterranean basin, the presence of the Pyrenees mountain range (with altitudes >3000 m), and the influence of the Mediterranean Sea and the large valley canalization of Ebro river induce an extremely complicated structure for the dispersion of photochemical pollutants. Air pollution studies in very complex terrains such as the NEIP require high-resolution modeling for resolving the very complex dynamics of flows. To deal with the influence of larger-scale transport, however, high-resolution models have to be nested in larger models to generate appropriate initial and boundary conditions for the finer resolution domains. This article shows the results obtained through the utilization of the MM5-EMICAT2000-CMAQ multiscale-nested air quality model relating the sensitivity regimes for ozone (O₃)-nitrogen oxides (NO_x)-volatile organic compounds (VOCs) in an area of high geographical complexity, like the industrial area of Tarragona, located in the NEIP. The model was applied with fine temporal (one-hour) and spatial resolution (cells of 24 km, 2 km, and 1 km) to represent the chemistry and transport of tropospheric O₃ and other photochemical species with respect to different hypothetical scenarios of emission controls and to quantify the influence of different emission sources in the area. Results indicate that O₃ chemistry in the industrial domain of Tarragona is strongly sensitive to VOCs; the higher percentages of reduction for ground-level O₃ are achieved when reducing by 25% the emissions of industrial VOCs. On the contrary, reductions in the industrial emissions of NO_x contribute to a strong increase in hourly peak levels of O₃. At the same time, the contribution of on-road traffic and biogenic emissions to ground-level O₃ concentrations in the area is negligible with respect to the pervasive weight of industrial sources. This analysis provides an assessment of the effectiveness of different policies for the control of emission of precursors by comparing the modeled results for different scenarios.     

Understanding the Effectiveness of Precursor Reductions in Lowering 8-Hr Ozone Concentrations—Part II. The Eastern United States

Abstract

Analyses of ozone (O₃) measurements in conjunction with photochemical modeling were used to assess the feasibility of attaining the federal 8-hr O₃ standard in the eastern United States. Various combinations of volatile organic compound (VOC) and oxides of nitrogen (NO_x) emission reductions were effective in lowering modeled peak 1-hr O₃ concentrations. VOC emissions reductions alone had only a modest impact on modeled peak 8-hr O₃ concentrations. Anthropogenic NO_x emissions reductions of 46–86% of 1996 base case values were needed to reach the level of the 8-hr standard in some areas. As NO_x emissions are reduced, O₃ production efficiency increases, which accounts for the less than proportional response of calculated 8-hr O₃ levels. Such increases in O₃ production efficiency also were noted in previous modeling work for central California. O₃ production in some urban core areas, such as New York City and Chicago, IL, was found to be VOC-limited. In these areas, moderate NO_x emissions reductions may be accompanied by increases in peak 8-hr O₃ levels. The findings help to explain differences in historical trends in 1- and 8-hr O₃ levels and have serious implications for the feasibility of attaining the 8-hr O₃ standard in several areas of the eastern United States.     

Analysis of the relationship between ambient levels of O3, NO2 and NO as a function of NOx in the UK

Monitoring data from the UK Automatic Urban and Rural Network are used to investigate the relationships between ambient levels of ozone (O₃), nitric oxide (NO) and nitrogen dioxide (NO₂) as a function of NO_x, for levels ranging from those typical of UK rural sites to those observed at polluted urban kerbside sites. Particular emphasis is placed on establishing how the level of ‘oxidant’, OX (taken to be the sum of O₃ and NO₂) varies with the level of NO_x, and therefore to gain some insight into the atmospheric sources of OX, particularly at polluted urban locations. The analyses indicate that the level of OX at a given location is made up of NO_x-independent and NO_x-dependent contributions. The former is effectively a regional contribution which equates to the regional background O₃ level, whereas the latter is effectively a local contribution which correlates with the level of primary pollution. The local oxidant source has probable contributions from (i) direct NO₂ emissions, (ii) the thermal reaction of NO with O₂ at high NO_x, and (iii) common-source emission of species which promote NO to NO₂ conversion. The final category may include nitrous acid (HONO), which appears to be emitted directly in vehicle exhaust, and is potentially photolysed to generate HO_x radicals on a short timescale throughout the year at southern UK latitudes. The analyses also show that the local oxidant source has significant site-to-site variations, and possible reasons for these variations are discussed. Relationships between OX and NO_x, based on annual mean data, and fitted functions describing the relative contributions to OX made by NO₂ and O₃, are used to define expressions which describe the likely variation of annual mean NO₂ as a function of NO_x at 14 urban and suburban sites, and which can take account of possible changes in the regional background of O₃.     

Factors influencing ozone chemistry in subsonic aircraft plumes

This study investigates several factors that could influence ozone chemistry occurring in subsonic aircraft plumes in the upper troposphere. The study focuses on uncertainties in gas-phase rate parameters, but also examines the influence of selected heterogeneous reactions, the rate of expansion of the plume, ambient and initial plume concentrations, and the time of emissions. Monte Carlo analysis with Latin hypercube sampling was applied to an expanding box model of an aircraft plume, in order to estimate the sensitivities of O₃ perturbations (ΔO₃) to uncertainties in rate constants in the RADM2 chemical mechanism. The resulting coefficient of variation in ΔO₃ at the end of a 36 h simulation was about 50%. Influential uncertainties in gas-phase rate parameters include those for photolysis of NO₂ and HCHO, O₃+NO, HO₂+NO, and formation of PAN and HNO₃. With high background concentrations of non-methane hydrocarbons, uncertainties in rate parameters of reactions involving peroxy radicals from ethene and propene oxidation were also influential. The coefficient of variation for ΔO₃ due to uncertainties in emission indices of NO_x, CO, and organic compounds was less than 15%. The effects of the heterogeneous reaction of N₂O₅ leading to HNO₃ formation, and hypothesized reactions of HNO₃ and NO₂ on soot, were also investigated. The results suggest that the latter two reactions could be influential for ΔO₃ if published estimates of reaction probabilities and high estimates of soot concentrations in plumes are realistic.     

Air Quality Modeling of Interpollutant Trading for Ozone Precursors in an Urban Area

Abstract

Emission trading is a market‐based approach designed to improve the efficiency and economic viability of emission control programs; emission trading has typically been confined to trades among single pollutants. Interpollutant trading (IPT), as described in this work, allows for trades among emissions of different compounds that affect the same air quality end point, in this work, ambient ozone (O₃) concentrations. Because emissions of different compounds impact air quality end points differently, weighting factors or trading ratios (tons of emissions of nitrogen oxides (NO_x) equivalent to a ton of emissions of volatile organic compounds [VOCs]) must be developed to allow for IPT. In this work, IPT indices based on reductions in O₃ concentrations and based on reductions in population exposures to O₃ were developed and evaluated using a three‐dimensional gridded photochemical model for Austin, TX, a city currently on the cusp of nonattainment with the National Ambient Air Quality Standards for O₃ concentrations averaged over 8 hr. Emissions of VOC and NO_x from area and mobile sources in Austin are larger than emissions from point sources. The analysis indicated that mobile and area sources exhibited similar impacts. Trading ratios based on maximum O₃ concentration or population exposure were similar. In contrast, the trading ratios did exhibit significant (more than a factor of two) day‐to‐day variability. Analysis of the air quality modeling indicated that the daily variability in trading ratios could be attributed to daily variations in both emissions and meteorology.     

Characterizations of chemical oxidants in Mexico City: A regional chemical dynamical model (WRF-Chem) study

The formation of chemical oxidants, particularly ozone, in Mexico City were studied using a newly developed regional chemical/dynamical model (WRF-Chem). The magnitude and timing of simulated diurnal cycles of ozone (O₃), carbon monoxide (CO) and nitrogen oxides (NO_x)_, and the maximum and minimum O₃ concentrations are generally consistent with surface measurements. Our analysis shows that the strong diurnal cycle in O₃ is mainly attributable to photochemical variations, while diurnal cycles of CO and NO_x mainly result from variations of emissions and boundary layer height. In a sensitivity study, oxidation reactions of aromatic hydrocarbons (HCs) and alkenes yield highest peak O₃ production rates (20 and 18 ppbv h⁻¹, respectively). Alkene oxidations, which are generally faster, dominate in early morning. By late morning, alkene concentrations drop, and oxidations of aromatics dominate, with lesser contributions from alkanes and CO. The sensitivity of O₃ concentrations to NO_x and HC emissions was assessed. Our results show that daytime O₃ production is HC-limited in the Mexico City metropolitan area, so that increases in HC emissions increase O₃ chemical production, while increases in NO_x emissions decrease O₃ concentrations. However, increases in both NO_x and HC emissions yield even greater O₃ increases than increases in HCs alone. Uncertainties in HC emissions estimates give large uncertainties in calculated daytime O₃, while NO_x emissions uncertainties are less influential. However, NO_x emissions are important in controlling O₃ at night.     

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.     

Estimating Taiwan biogenic VOC emission: Leaf energy balance consideration

The goal of the present study is to provide a comprehensive model to estimate biogenic volatile organic compounds (BVOCs) in Taiwan. In addition to metrological data, the model consists of (1) 83 land-use patterns, (2) emission factors for various vegetations, (3) energy balance equation to account for leaf temperature, and (4) correction terms for photosynthetically active radiation. The model output includes 4 categories of 33 BVOCs [isoprene, methylbutenol (MBO), 14 species of monoterpenes and 17 other BVOCs]. The results of model verification based on several approaches include: (1) predicted isoprene emission flux correlates relatively good with the observed isoprene concentration (R² = 0.66); (2) correlation between leaf temperature and observed isoprene levels is better than that between ambient temperature and isoprene concentrations (R² = 0.63 vs. 0.58); (3) model-predicted isoprene fluxes match well with observed 3-day diurnal isoprene concentration variations; and (4) subsequent model-predicted O₃ concentrations with the BVOC input obtained in the present study match well than that with previous estimated BVOC data with the observed 6-day diurnal O₃ levels in 8 air quality monitoring stations.Based on the meteorological data in 2000, the total emission of BVOCs in Taiwan was simulated to be about 433,000 ton (33% of total VOCs) of which both isoprene and 14 species of monoterpenes account for about 34%, with 17 species of other BVOCs being 31% and <2% contribution from MBO. Total emissions of BVOCs are higher in lower and medium altitude (300–1000 m) mountain areas with an average of around 15–30 ton km⁻² y⁻¹. The implication of the other results is also discussed.     

High NOx levels and lack of ozone in downtown Caracas

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

Emissions Variability Processor (EMVAP): Design,evaluation, and application

Emissions of pollutants such as SO₂ and NOx from external combustion sources can vary widely depending on fuel sulfur content, load, and transient conditions such as startup, shutdown, and maintenance/malfunction. While monitoring will automatically reflect variability from both emissions and meteorological influences, dispersion modeling has been typically conducted with a single constant peak emission rate. To respond to the need to account for emissions variability in addressing probabilistic 1-hr ambient air quality standards for SO₂ and NO₂, we have developed a statistical technique, the Emissions Variability Processor (EMVAP), which can account for emissions variability in dispersion modeling through Monte Carlo sampling from a specified frequency distribution of emission rates. Based upon initial AERMOD modeling of from 1 to 5 years of actual meteorological conditions, EMVAP is used as a postprocessor to AERMOD to simulate hundreds or even thousands of years of concentration predictions. This procedure uses emissions varied hourly with a Monte Carlo sampling process that is based upon the user-specified emissions distribution, from which a probabilistic estimate can be obtained of the controlling concentration. EMVAP can also accommodate an advanced Tier 2 NO₂ modeling technique that uses a varying ambient ratio method approach to determine the fraction of total oxides of nitrogen that are in the form of nitrogen dioxide. For the case of the 1-hr National Ambient Air Quality Standards (NAAQS, established for SO₂ and NO₂), a “critical value” can be defined as the highest hourly emission rate that would be simulated to satisfy the standard using air dispersion models assuming constant emissions throughout the simulation. The critical value can be used as the starting point for a procedure like EMVAP that evaluates the impact of emissions variability and uses this information to determine an appropriate value to use for a longer term (e.g., 30-day) average emission rate that would still provide protection for the NAAQS under consideration. This paper reports on the design of EMVAP and its evaluation on several field databases that demonstrate that EMVAP produces a suitably modest overestimation of design concentrations. We also provide an example of an EMVAP application that involves a case in which a new emission limitation needs to be considered for a hypothetical emission unit that has infrequent higher-than-normal SO₂ emissions.

ImplicationsEmissions of pollutants from combustion sources can vary widely depending on fuel sulfur content, load, and transient conditions such as startup and shutdown. While monitoring will automatically reflect this variability on measured concentrations, dispersion modeling is typically conducted with a single peak emission rate assumed to occur continuously. To realistically account for emissions variability in addressing probabilistic 1-hr ambient air quality standards for SO₂ and NO₂, the authors have developed a statistical technique, the Emissions Variability Processor (EMVAP), which can account for emissions variability in dispersion modeling through Monte Carlo sampling from a specified frequency distribution of emission rates.     

Estimation and validation of PM2.5/PM10 exhaust and non-exhaust emission factors for practical street pollution modelling

In order to carry out efficient traffic and air quality management, validated models and PM emission estimates are needed. This paper compares current available emission factor estimates for PM₁₀ and PM_2.5 from emission databases and different emission models, and validates these against eight high quality street pollution measurements in Denmark, Sweden, Germany, Finland and Austria.The data sets show large variation of the PM concentration and emission factors with season and with location. Consistently at all roads the PM₁₀ and PM_2.5 emission factors are lower in the summer month than the rest of the year. For example, PM₁₀ emission factors are in average 5–45% lower during the month 6–10 compared to the annual average.The range of observed total emission factors (including non-exhaust emissions) for the different sites during summer conditions are 80–130 mg km⁻¹ for PM₁₀, 30–60 mg km⁻¹ for PM_2.5 and 20–50 mg km⁻¹ for the exhaust emissions.We present two different strategies regarding modelling of PM emissions: (1) For Nordic conditions with strong seasonal variations due to studded tyres and the use of sand/salt as anti-skid treatment a time varying emission model is needed. An empirical model accounting for these Nordic conditions was previously developed in Sweden. (2) For other roads with a less pronounced seasonal variation (e.g. in Denmark, Germany, Austria) methods using a constant emission factor maybe appropriate. Two models are presented here.Further, we apply the different emission models to data sets outside the original countries. For example, we apply the “Swedish” model for two streets without studded tyre usage and the “German” model for Nordic data sets. The “Swedish” empirical model performs best for streets with studded tyre use, but was not able to improve the correlation versus measurements in comparison to using constant emission factors for the Danish side. The “German” method performed well for the streets without clear seasonal variation and reproduces the summer conditions for streets with pronounced seasonal variation. However, the seasonal variation of PM emission factors can be important even for countries not using studded tyres, e.g. in areas with cold weather and snow events using sand and de-icing materials. Here a constant emission factor probably will under-estimate the 90-percentiles and therefore a time varying emission model need to be used or developed for such areas.All emission factor models consistently indicate that a large part (about 50–85% depending on the location) of the total PM₁₀ emissions originates from non-exhaust emissions. This implies that reduction measures for the exhaust part of the vehicle emissions will only have a limited effect on ambient PM₁₀ levels.     

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

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