Formation and Transport of the Madrid Ozone Plume

Abstract

The main results of an experimental study focusing on the formation and transport of photochemical pollution in the Madrid air basin are presented. This southern European, heavily populated urban area is located on an elevated plateau at a height of 700 m, near a mountain range with maximum heights of around 2,400 m. Daily and seasonal cycles of ozone were documented during a one-year survey at three semi-rural sites located 30 km away from the urban center. Maximum hourly values of up to 140 ppb were measured, and the ozone generated within the urban plume on polluted days (when values exceeded 90 ppb) has been estimated at around 40-50 ppb.A meteorological characterization of these smoggy days pointed out the influence of thermally induced local wind flows on the concentration daily cycles at the measuring sites, denoting a preferred advection of the urban plume. Moreover, during intensive summer field campaigns, the use of meteorological and ozone sondes, as well as an instrumented aircraft, revealed some features about the horizontal and vertical distribution of the polluted air masses, as well as their evolution within the planetary boundary layer. Ozone plumes have been detected up to 100 km away from the city, usually mixed in a layer that reaches a height of 1,000-1,500 m in the afternoon. On some occasions, ozone-enriched layers have been detected as high as 4,000 m during morning hours, suggesting possible tropospheric injection induced by topographydriven flows or convective mesoscale systems that are usually present in the center of the Iberian Peninsula in the summer.     

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.     

Emission Strength Validation Using Four-Dimensional Data Assimilation: Application to Primary Aerosol and Precursors to Ozone and Secondary Aerosol

ABSTRACT

Three-dimensional air quality models (AQMs) represent the most powerful tool to follow the dynamics of air pollutants at urban and regional scales. Current AQMs can account for the complex interactions between gas-phase chemistry, aerosol growth, cloud and scavenging processes, and transport. However, errors in model applications still exist due in part to limitations in the models themselves and in part to uncertainties in model inputs. Four-dimensional data assimilation (FDDA) can be used as a top-down tool to validate several of the model inputs, including emissions inventories, based on ambient measurements. Previously, this FDDA technique was used to estimate adjustments in the strength and composition of emissions of gas-phase primary species and O₃ precursors.

In this paper, we present an extension to the FDDA technique to incorporate the analysis of particulate matter (PM) and its precursors. The FDDA approach consists of an iterative optimization procedure in which an AQM is coupled to an inverse model, and adjusting the emissions minimizes the difference between ambient measurements     

California Statewide Assessment of the Effects of Ozone on Crop Productivity

Six properties appear desirable for any set of ozone attainment criteria: (1) sufficient stringency to protect public health, (2) simplicity and understandability, (3) sensitivity to real changes in air quality, (4) stability against meteorological fluctuations, (5) use of as much data as possible, and (6) equivalence between the stringency the criteria appear to mandate, and what they actually mandate. We consider how the federal attainment criteria might be improved with respect to Properties 4 through 6 while being equally strong on 1 through 3. Whether the federal standard meets Property 1 has been the subject of debate, but our analysis would apply also to a modified standard. We show that there are subtleties in how improvements might be made. In particular, basing the attainment status on a statistic with low variance may not lead to a more stable criterion, and although it is easy to find a criterion that makes it hard for a district with bad air to reach attainment, or a district with good air to get out of attainment, it is hard to find a criterion that does both. This suggests using different criteria for districts that are out of attainment from districts that are in attainment. Initially the burden of proof would be on the district to prove that its air is of attainment quality. However, once the district has achieved attainment the burden of proof would shift; the district would remain in attainment unless there was strong evidence to the contrary. An evaluation of a set of criteria based on this idea showed improvements over the federal criteria with respect to the last three desirable properties-stability, use of data, and equivalent stringency-with some sacrifice in simplicity and sensitivity.     

Effects of Constant versus Diurnally-Varying Light Intensity on Ozone Formation

Abstract

1-Bromo-propane (1-BP) is a replacement for high-end chlorofluorocarbon (HCFC) solvents. Its reaction rate constant with the OH radical is, on a weight basis, significantly less than that of ethane. However, the overall smog formation chemistry of 1-BP appears to be very unusual compared with typical volatile organic compounds (VOCs) and relatively complex because of the presence of bromine. In smog chamber experiments, 1-BP initially shows a faster ozone build-up than what would be expected from ethane, but the secondary products containing bromine tend to destroy ozone such that 1-BP can have a net overall negative reactivity. Alternative sets of reactions are offered to explain this unusual behavior. Follow-up studies are suggested to resolve the chemistry. Using one set of bromine-related reactions in a photo-chemical grid model shows that 1-BP would be less reactive toward peak ozone formation than ethane with a trend toward even lower ozone impacts in the future.     

A Reassessment of the Economic Effects of Ozone on U.S. Agriculture

The potential adverse effects of environmental change on agriculture have motivated considerable public research on this topic. Acid deposition, gaseous air pollutants, stratosphere ozone depletion and "green house" phenomena, individually and in combination, have been or are being evaluated in terms of effects on agricultural productivity. Assessments of the economic consequences of such effects have also been performed as input into the regulatory process. As with any applied bioeconomic analysis, the credibility of these economic assessments is dependent on the quality of the natural science and other data on the pollutant In question.

The ability of economists to assess the agricultural effects of one important pollutant, tropospheric ozone, has been Improved by the recently completed National Crop Loss Assessment Network (NCLAN). The structure, protocols and initial plant science findings of this U.S. Environmental Protection Agency program have been presented in this journal (see, for example, Heck et al).^1-2 In a related article,³ we reported the economic consequences of those preliminary ozone crop yield effects. Summary plant science findings have now been published.⁴

We provide here a more complete analysis of estimated benefits from reductions in troposphere ozone based on the final results of the NCLAN plant science research. In doing so, we concentrate on improvements in the modeling and underlying data which are reflected In this current assessment. While uncertainties still remain, these improvements should result in more defensible estimates of the magnitude of ozone’s effects on U.S. agriculture.     

An Assessment of the Economic Effects of Ozone on U.S. Agriculture

Past attempts to measure the economic consequences of ozone on agriculture have been based on limited plant science information. This paper reports on an economic assessment of ozone on U.S. agriculture using recent crop response data from the National Crop Loss Assessment Network (NCLAN). The results are derived from a U.S. agricultural sector model that includes major crop and livestock production as well as domestic consumption, livestock feeding and export uses. The economic effects of four hypothetical ambient ozone levels are investigated. The analysis Indicates that the benefits to society of moderate (25%) ozone reductions are approximately $1.7 billion. A 25% Increase in ozone pollution results in costs (negative benefits) of $2.1 billion. These estimates do not reflect compliance costs of achieving the ozone changes and hence are not net benefits.     

Prediction of the Vertical Profile of Ozone Based on Ground-Level Ozone Observations and Cloud Cover

Abstract

A number of statistical techniques have been used to develop models to predict high-elevation ozone (O₃) concentrations for each discrete hour of day as a function of elevation based on ground-level O₃ observations. The analyses evaluated the effect of exclusion/inclusion of cloud cover as a variable. It was found that a simple model, using the current maximum ground-level O₃ concentration and no effect of cloud cover provided a reasonable prediction of the vertical profile of O₃, based on data analyzed from O₃ sites located in North Carolina and Tennessee. The simple model provided an approach that estimates the concentration of O₃ as a function of elevation (up to 1800 m) based on the statistical results with a ±13.5 ppb prediction error, an R² of 0.56, and an index of agreement, d ₁, of 0.66. The inclusion of cloud cover resulted in a slight improvement in the model over the simple regression model. The developed models, which consist of two matrices of 24 equations (one for each hour of day for clear to partly cloudy conditions and one for cloudy conditions), can be used to estimate the vertical O₃ profile based on the inputs of the current day’s 1-hr maximum ground-level O₃ concentration and the level of cloud cover.     

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.     

Ozone Predictions in Atlanta,Georgia: Analysis of the 1999 Ozone Season

ABSTRACT

Ozone prediction has become an important activity in many U.S. ozone nonattainment areas. In this study, we describe the ozone prediction program in the Atlanta metropolitan area and analyze the performance of this program during the 1999 ozone-forecasting season. From May to September, a team of 10 air quality regulators, meteorologists, and atmospheric scientists made a daily prediction of the next-day maximum 8-hr average ozone concentration. The daily forecast was made aided by two linear regression models, a 3-dimensional air quality model, and the no-skill ozone persistence model. The team's performance is compared with the numerical models using several numerical indicators. Our analysis indicated that (1) the team correctly predicted next-day peak ozone concentrations 84% of the time, (2) the two linear regression models had a better performance than a 3-dimensional air quality model, (3) persistence was a strong predictor of ozone concentrations with a performance of 78%, and (4) about half of the team's wrong predictions could be prevented with improved meteorological predictions.     

The Sensitivity of PM25 Source-Receptor Relationships to Atmospheric Chemistry and Transport in a Three-Dimensional Air Quality Model

ABSTRACT

Air quality model simulations constitute an effective approach to developing source-receptor relationships (so-called transfer coefficients in the risk analysis framework) because a significant fraction of particulate matter (particularly PM_2.5) is secondary (i.e., formed in the atmosphere) and, therefore, depends on the atmospheric chemistry of the airshed. In this study, we have used a comprehensive three-dimensional air quality model for PM_{2 5} (SAQM-AERO) to compare three approaches to generating episodic transfer coefficients for several source regions in the Los Angeles Basin. First, transfer coefficients were developed by conducting PM_2.5 SAQM-AERO simulations with reduced emissions of one of four precursors (i.e., primary PM, sulfur dioxide (SO₂), oxides of nitrogen (NO_x), and volatile organic compounds) from each source region. Next, we calculated transfer coefficients using two other methods: (1) a simplified chemistry for PM_2.5 formation, and (2) simplifying assumptions on transport using information limited to basin-wide emission reductions. Transfer coefficients obtained with the simplified chemistry were similar to those obtained with the comprehensive model for VOC emission changes but differed for NO and SO emission changes. The differences were due to the parameterization of the rates of secondary PM formation in the simplified chemistry. In 90% of the cases, transfer coefficients estimated using only basin-wide information were within a factor of two of those obtained with the explicit source-receptor simulations conducted with the comprehensive model. The best agreement was obtained for VOC emission changes; poor agreement was obtained for primary PM_2.5.     

The Characterization of Ozone and Sulfur Dioxide Air Quality Data for Assessing Possible Vegetation Effects

Since the 1960s, much effort has been devoted to collecting and formatting air quality data. This paper discusses 1) the availability of air quality data for assessing potential biological impacts associated with ozone and sulfur dioxide ambient exposures, 2) examples of how air quality data can be characterized for assessing vegetation effects, and 3) the limitations associated with some exposure parameters used for developing relevant vegetation doseresponse yield reduction models. Data are presented showing that some ozone monitoring sites not continuously affected by local urban sources experience consecutive hourly ozone exposures ≥0.10 ppm in the late evening and early morning hours. These sites experience their maximum ozone concentrations either in the spring or summer months. Sites influenced by local rural sources experience their maximum ozone concentrations during the summer months. It is suggested that further research be performed to identify whether the sensitivity of a target organism at the time of exposure, as well as the pollutant concentration and chemical form that enters into the target organism, is as important in defining effects as air pollutant exposure alone.     

The Effect of NMOC and Ozone Aloft on Modeled Urban Ozone Production and Control Strategies

Carbon bond (CB-III) fractions for non-methane organic carbon compounds (NMOC) measured in the background alrmass adverted into several urban areas in the eastern and southern United States are reported. These, together with ozone measured aloft, were used In an Empirical Kinetic Modeling Approach (EKMA) to model urban ozone production and urban ozone control strategies.

Over a range of zero to double the mean of the measured NMOC concentrations aloft (0 to 70 ppbC) and zero to the highest ozone levels recorded aloft (0 to 65 ppb), it was found that urban ozone production and control strategies were relatively insensitive to NMOC from aloft. However, urban ozone production was sensitive to ozone from aloft, while ozone control strategies were insensitive to ozone from aloft.     

Modeling the Effects of VOC/NOx Emissions on Ozone Synthesis in the Cascadia Airshed of the Pacific Northwest

ABSTRACT

A modeling system consisting of MM5, Calmet, and Calgrid was used to investigate the sensitivity of anthropogenic volatile organic compound (VOC) and oxides of nitrogen (NO_x) reductions on ozone formation within the Cascadia airshed of the Pacific Northwest. An ozone episode that occurred on July 11-14, 1996, was evaluated. During this event, high ozone levels were recorded at monitors downwind of Seattle, WA, and Portland, OR, with one monitor exceeding the 1 hr/120 ppb National Ambient Air Quality Standard (at 148 ppb), and six monitors above the proposed 8 hr/80 ppb standard (at 82-130 ppb). For this particular case, significant emissions reductions, between 25 and 75%, would be required to decrease peak ozone concentrations to desired levels. Reductions in VOC emissions alone, or a combination of reduced VOC and NO_x emissions, were generally found to be most effective; reducing NO_x emissions alone resulted in increased ozone in the Seattle area. When only VOC emissions were curtailed, ozone reductions occurred in the immediate vicinity of densely populated areas, while NO_x reductions resulted in more widespread ozone reductions.     

Ozone and the clean troposphere: ecological implications

In recent years numerous investigations have examined the relationships between chronic ozone (O(3)) exposure and plant responses using statistical or empirical cause-effect models. One of the critically important decisions underlying these studies has been the choice of the control or reference O(3) exposure to which all other treatments are compared. The issue of the control or reference O(3) exposure is a complex one. Does a single ambient control or reference O(3) exposure exist? The approach taken in this paper is to examine the O(3) concentrations in the 'clean troposphere.' One must ask what a clean troposphere is and whether there are any geographic locations in the world today that are totally free of human influences. Data on photochemical oxidants from Fortress Mountain, Alberta, Canada, are examined. A comparison of these data with air quality data from other locations in North America is used to examine the design of vegetation response studies. The need for integrated research design, execution, and evaluation is stressed.     

Effects of Chronic Doses of Ozone on Field-Grown Loblolly Pine: Seedling Responses in the First Year

A study was designed to examine responses of loblolly pine (Pinus taeda) to chronic exposure to ozone (O₃) in the field. Seedlings of four full-sib families of loblolly pine were planted in a field near Raleigh, NC, and exposed daily (May 27 to October 24, 1985) in open-top chambers to O₃ ranging from 0.5 to 1.96 times the O₃ concentration in non-filtered (NF) air. One-fourth of the plants in each plot were removed during each of two harvests (August and October) to measure effects of O₃ on plant growth. Plants of each family exhibited foliar symptoms characteristic of O3 injury after five months of exposure to any greater-than-ambient O₃ concentration, and one family exhibited symptoms after five months of exposure to NF air. Ozone dose-plant response relationships were quantified by regression for stem height, stem diameter, biomass, and other plant morphological and yield characteristics. All relationships were linear for three families, but one family exhibited no significant growth response relationship of O₃ dose. Dose-response equations suggest a maximum growth suppression of 10 percent for NF air compared to charcoal-filtered air (i.e., 0.5 × NF) in the first season of exposure.     

Attainment Flip-Flops and the Achievability of the Ozone Air Quality Standard

Abstract

This paper presents the results of the first reported study on fine particulate matter (PM) chemical composition at Salamanca, a highly industrialized urban area of Central Mexico. Samples were collected at six sites within the urban area during February and March 2003. Several trace elements, organic carbon (OC), elemental carbon (EC), and six ions were analyzed to characterize aerosols. Average concentrations of PM with aerodynamic diameter of less than 10 μm (PM₁₀) and fine PM with aerodynamic diameter of less than 2.5 μm (PM_2.5) ranged from 32.2 to 76.6 μg m^-3 and 11.1 to 23.7 μg m^-3, respectively. OC (34%), SO₄ ⁼ (25.1%), EC (12.9%), and geological material (12.5%) were the major components of PM_2.5. For PM₁₀, geological material (57.9%), OC (17.3%), and SO₄ ⁼ (9.7%) were the major components. Coarse fraction (PM₁₀ –PM_2.5), geological material (81.7%), and OC (8.6%) were the dominant species, which amounted to 90.4%. Correlation analysis showed that sulfate in PM_2.5 was present as ammonium sulfate. Sulfate showed a significant spatial variation with higher concentrations to the north resulting from predominantly southwesterly winds above the surface layer and by major SO₂ sources that include a power plant and refinery. At the urban site of Cruz Roja it was observed that PM_2.5 mass concentrations were similar to the submicron fraction concentrations. Furthermore, the correlation between EC in PM_2.5 and EC measured from an aethalometer was r² = 0.710. Temporal variations of SO₂ and nitrogen oxide were observed during a day when the maximum concentration of PM_2.5 was measured, which was associated with emissions from the nearby refinery and power plant. From cascade impactor measurements, the three measured modes of airborne particles corresponded with diameters of 0.32, 1.8, and 5.6 μm.     

Effects of soil type upon metolachlor losses in subsurface drainage

A field experiment at La Bouzule (Lorraine, France) investigated metolachlor movement to subsurface drains in two soil types, a silt loam and a heavy clay soil, under identical agricultural management practices and climatic conditions. Drainage volumes and concentrations of metolachlor in the soil plough layer and drainwater were monitored after herbicide application from May 1996 to February 1997, and from May to August 1998. Total losses in drainwater were 0.08% and 0.18% of the amount applied to the silt loam compared with 0.59% and 0.41% for the clay soil, in 1996/97 and 1998, respectively. In 1996/97, 32% of total metolachlor loss from the silt loam and 91% from the clay soil occurred during the spring/summer period following treatment. Peak concentrations were 18.5 and 171.6 microg l(-1) for the silt loam and 130.6 and 395.3 microg l(-1) for the clay soil during the spring/summer periods of 1996/97 and 1998, respectively. During the autumn/winter period, concentrations did not exceed 2.2 microg l(-1) for the silt loam and 2.6 microg l(-1) for the clay soil. The experimental results indicate that metolachlor losses in drainwater were primarily caused by preferential flow (macropore flow) which was greater in the clay soil than in the silt loam, and occurring mainly during the spring/summer periods.     

Cloud Albedo,Greenhouse Effects,Atmospheric Chemistry,and Climate Change

Changes in global atmospheric chemistry and climate are taking place as a result of observed trends in long-lived species such as CO₂, CH₄, N₂O, and the CFCs. The continuation of these trends is expected to eventually lead to a major atmospheric warming that might profoundly affect the society we live in. Trends in short-lived species such as NOx and SOx are also suspected. These trends are not as well established, because the shorter-lived species vary spatially and temporally. Trends in NOx would be expected to lead to increases in tropospheric ozone that would add to the warming created by the other greenhouse gases. Trends in NOx could also alter tropospheric OH concentrations that could lead to changes in CH₄ and some of the CFCs. On the other hand, increases in sulfur emissions may alter cloud optical properties. The changes in cloud optical properties could possibly offset the warming expected from increases in greenhouse gases, depending on the role of natural oceanic sulfur emissions. This paper summarizes recent research in these areas and the interactions of climate and atmospheric chemistry.