Characterization of PM25 and PM10 in the South Coast Air Basin of Southern California: Part 2—Temporal Variations

ABSTRACT

The South Coast Air Quality Management District (SCAQMD) conducted a 1-year special particulate monitoring study from January 1995 to February 1996. This monitoring data indicates that high PM₁₀ and PM_{2 5} concentrations were observed in the fall (October, November, and December), with November concentrations being the highest. During the rest of the year, PM_2.5 and PM₁₀ masses gradually increased from January to September. Monthly PM₁₀ mass varied from 20 to 120 |ig/m³, and monthly PM₂₅ mass varied from 13 to 63 |j.g/m³. The PM_2.5-to-PM₁₀ ratio varied daily and ranged between 22 and 96%. Two types of high-PM days were observed. The first type was observed under fall stagnation conditions, which lead to high secondary species concentrations. The second type was observed under high wind conditions, which lead to high primary coarse particles of crustal components. The highest 24-hr average PM₁₀ concentration (226.3 |ig/m³) was observed at the Fontana station, while the highest PM₂₅ concentration (129.3 |ig/m³) was observed at the Diamond Bar station.     

Diurnal and Weekday Variations in the Source Contributions of Ozone Precursors in California’s South Coast Air Basin

Abstract

For at least 30 years, ozone (O₃) levels on weekends in parts of California’s South Coast (Los Angeles) Air Basin (SoCAB) have been as high as or higher than on weekdays, even though ambient levels of O₃ precursors are lower on weekends than on weekdays. A field study was conducted in the Los Angeles area during fall 2000 to test whether proposed relationships between emission sources and ambient nonmethane hydrocarbon (NMHC) and oxides of nitrogen (NO_x) levels can account for observed diurnal and day-of-week variations in the concentration and proportions of precursor pollutants that may affect the efficiency and rate of O₃ formation. The contributions to ambient NMHC by motor vehicle exhaust and evaporative emissions, estimated using chemical mass balance (CMB) receptor modeling, ranged from 65 to 85% with minimal day-of-week variation. Ratios of ambient NO_x associated with black carbon (BC) to NO_x associated with carbon monoxide (CO) were approximately 1.25 ± 0.22 during weekdays and 0.76 ± 0.07 and 0.52 ± 0.07 on Saturday and Sunday, respectively. These results demonstrate that lower NO_x emissions from diesel exhaust can be a major factor causing lower NO_x mixing ratios and higher NMHC/NO_x ratios on weekends. Nonmobile sources showed no significant day-of-week variations in their contributions to NMHC. Greater amounts of gasoline emissions are carried over on Friday and Saturday evenings but are, at most, a minor factor contributing to higher NMHC/NO_x ratios on weekend mornings.     

Air quality modeling in the South Coast Air Basin of California: what do the numbers really mean?

This study evaluates air quality model sensitivity to input and to model components. Simulations are performed using the California Institute of Technology (CIT) airshed model. Results show the impacts on ozone (O3) concentration in the South Coast Air Basin (SCAB) of California because of changes in: (1) input data, including meteorological conditions (temperature, UV radiation, mixing height, and wind speed), boundary conditions, and initial conditions (ICs); and (2) model components, including advection solver and chemical mechanism. O3 concentrations are strongly affected by meteorological conditions and, in particular, by temperature. ICs also affect O3 concentrations, especially in the first 2 days of simulation. On the other hand, boundary conditions do not significantly affect the absolute peak O3 concentration, although they do affect concentrations near the inflow boundaries. Moreover, predicted O3 concentrations are impacted considerably by the chemical mechanism. In addition, dispersion of pollutants is affected by the advection routine used to calculate its transport. Comparison among CIT, California Photochemical Grid Model (CALGRID), and Urban Airshed Model air quality models suggests that differences in O3 predictions are mainly caused by the different chemical mechanisms used. Additionally, advection solvers contribute to the differences observed among model predictions. Uncertainty in predicted peak O3 concentration suggests that air quality evaluation should not be based solely on this single value but also on trends predicted by air quality models using a number of chemical mechanisms and with an advection solver that is mass conservative.     

Air Quality Modeling in the South Coast Air Basin of California: What Do the Numbers Really Mean?

Abstract

This study evaluates air quality model sensitivity to input and to model components. Simulations are performed using the California Institute of Technology (CIT) airshed model. Results show the impacts on ozone (O₃) concentration in the South Coast Air Basin (SCAB) of California because of changes in: (1) input data, including meteorological conditions (temperature, UV radiation, mixing height, and wind speed), boundary conditions, and initial conditions (ICs); and (2) model components, including advection solver and chemical mechanism. O₃ concentrations are strongly affected by meteorological conditions and, in particular, by temperature. ICs also affect O₃ concentrations, especially in the first 2 days of simulation. On the other hand, boundary conditions do not significantly affect the absolute peak O₃ concentration, although they do affect concentrations near the inflow boundaries. Moreover, predicted O₃ concentrations are impacted considerably by the chemical mechanism. In addition, dispersion of pollutants is affected by the advection routine used to calculate its transport. Comparison among CIT, California Photochemical Grid Model (CALGRID), and Urban Airshed Model air quality models suggests that differences in O₃ predictions are mainly caused by the different chemical mechanisms used. Additionally, advection solvers contribute to the differences observed among model predictions. Uncertainty in predicted peak O₃ concentration suggests that air quality evaluation should not be based solely on this single value but also on trends predicted by air quality models using a number of chemical mechanisms and with an advection solver that is mass conservative.     

Evolution of the Magnitude and Spatial Extent of the Weekend Ozone Effect in California’s South Coast Air Basin, 1981–2000

Abstract

Since the mid-1970s, ozone (O₃) levels in portions of California’s South Coast Air Basin (SoCAB) on weekends have been as high as or higher than levels on weekdays, even though emissions of O₃ precursors are lower on weekends. Analysis of the ambient data indicates that the intensity and spatial extent of the weekend O₃ effect are correlated with day-of-week variations in the extent of O₃ inhibition caused by titration with nitric oxide (NO), reaction of hydroxyl radical (OH) with nitrogen dioxide (NO₂), and rates of O₃ accumulation. Lower NO mixing ratios and higher NO₂/oxides of nitrogen (NO_x) ratios on weekend mornings allow O₃ to begin accumulating approximately an hour earlier on weekends. The weekday/weekend differences in the duration of O₃ accumulation remained relatively constant from 1981 to 2000. In contrast, the rate of O₃ accumulation decreased by one-third to one-half over the same period; the largest reductions occurred in the central basin on weekdays. Trends in mixing ratios of O₃ precursors show a transition to lower volatile organic compound (VOC)/NO_x ratios caused by greater reductions in VOC emissions. Reductions in VOC/NO_x ratios were greater on weekdays, resulting in higher VOC/NO_x ratios on weekends relative to weekdays. Trends in VOC/NO_x ratios parallel the downward trend in peak O₃ levels, a shift in the location of peak O₃ from the central to the eastern portion of the basin, and an increase in the magnitude and spatial extent of the weekend O₃ effect.     

Particulate Matter in California: Part 2—Spatial,Temporal, and Compositional Patterns of PM2.5, PM10–2.5, and PM10

Abstract

Geographic and temporal variations in the concentration and composition of particulate matter (PM) provide important insights into particle sources, atmospheric processes that influence particle formation, and PM management strategies. In the nonurban areas of California, annual-average PM_2.5 and PM₁₀ concentrations range from 3 to 10 [H9262]g/m³ and from 5 to 18 µg/m³, respectively. In the urban areas of California, annual-averages for PM_2.5 range from 7 to 30 [H9262]g/m³, with observed 24-hr peaks reaching levels as high as 160 [H9262]g/m³. Within each air basin, exceedances are a mixture of isolated events as well as periods of elevated PM_2.5 concentrations that are more prolonged and regional in nature. PM_2.5 concentrations are generally highest during the winter months. The exception is the South Coast Air Basin, where fairly high values occur throughout the year. Annual-average PM_2.5 mass, as well as the concentrations of major components, declined from 1988 to 2000. The declines are especially pronounced for the sulfate (SO₄ ^2?) and nitrate (NO₃ ^?) components of PM_2.5 and PM₁₀ and correlate with reductions in ambient levels of oxides of sulfur (SO_x) and oxides of nitrogen (NO_x). Annual averages for PM_10–2.5 and PM₁₀ exhibited similar downwind trends from 1994 to 1999, with a slightly less pronounced decrease in the coarse fraction.     

Particulate Matter in California: Part 1—Intercomparison of Several PM2.5, PM10–2.5, and PM10 Monitoring Networks

Abstract

It will be many years before the recently deployed network of fine particulate matter with an aerodynamic diameter less than 2.5 [H9262]m (PM_2.5) Federal Reference Method (FRM) samplers produces information on nonattainment areas, trends, and source impacts. However, data on PM_2.5 and its major constituents have been routinely collected in California for the past 20 years. The California Air Resources Board operated as many as 20 dichotomous (dichot) samplers for PM_2.5 and coarse PM (PM_10–2.5). The California Acid Deposition Monitoring Program (CADMP) collected 12-h-average PM_2.5 and PM₁₀ from 1988 to 1995 at ten urban and rural sites and 24-h-average PM_2.5 at five urban sites since 1995. Beginning in 1994, the Children’s Health Study collected 2-week averages of PM_2.5 in 12 communities in southern California using the Two-Week Sampler (TWS). Comparisons of collocated samples establish relationships between the dichot, CADMP, and TWS samplers and the 82-site network of PM_2.5 FRM samplers deployed since 1999 in California. PM mass data from the different monitoring programs have modest to high correlation to FRM mass data, fairly small systematic biases and negative proportional biases ranging from 7 to 22%. If the biases are taken into account, all of the programs should be considered comparable with the FRM program. Thus, historical data can be used to develop long-term PM trends in California.     

The Southeastern Aerosol Research and Characterization Study: Part 1—Overview

Abstract

This paper presents an overview of a major, long-term program for tropospheric gas and aerosol research in the southeastern United States. Building on three existing ozone (O₃)-focused research sites begun in mid-1992, the Southeastern Aerosol Research and Characterization Study (SEARCH) was initiated in mid-1998 as a 7-year observation and research program with a broader focus including aerosols and an expanded geographical coverage in the Southeast. The monitoring network comprises four urban-rural (or urban-suburban) site pairs at locations along the coast of the Gulf of Mexico and inland, including two moderately sized and two major urban areas (Pensacola, FL; Gulfport, MS; Atlanta, GA; and Birmingham, AL). The sites are equipped with an extensive suite of instruments for measuring particulate matter (PM), gases relevant to secondary O₃ and the production of secondary aerosol particles, and surface meteorology. The measurements taken to date have added substantially to the knowledge about the temporal behavior and geographic variability of tropospheric aerosols in the Southeast. Details are presented in four papers to follow.     

Modeling air quality during the California Regional PM10/PM2.5 Air Quality Study (CPRAQS) using the UCD/CIT source-oriented air quality model – Part III. Regional source apportionment of secondary and total airborne particulate matter

A comprehensive air quality modeling project was carried out to simulate regional source contributions to secondary and total (=primary + secondary) airborne particle concentrations in California's Central Valley. A three-week stagnation episode lasting from December 15, 2000 to January 7, 2001, was chosen for study using the air quality and meteorological data collected during the California Regional PM₁₀/PM_2.5 Air Quality Study (CRPAQS). The UCD/CIT mechanistic air quality model was used with explicit decomposition of the gas phase reaction chemistry to track source contributions to secondary PM. Inert artificial tracers were used with an internal mixture representation to track source contributions to primary PM. Both primary and secondary source apportionment calculations were performed for 15 size fractions ranging from 0.01 to 10 μm particle diameters. Primary and secondary source contributions were resolved for fugitive dust, road dust, diesel engines, catalyst equipped gasoline engines, non-catalyst equipped gasoline engines, wood burning, food cooking, high sulfur fuel combustion, and other anthropogenic sources.Diesel engines were identified as the largest source of secondary nitrate in central California during the study episode, accounting for approximately 40% of the total PM_2.5 nitrate. Catalyst equipped gasoline engines were also significant, contributing approximately 20% of the total secondary PM_2.5 nitrate. Agricultural sources were the dominant source of secondary ammonium ion. Sharp gradients of PM concentrations were predicted around major urban areas. The relative source contributions to PM_2.5 from each source category in urban areas differ from those in rural areas, due to the dominance of primary OC in urban locations and secondary nitrate in the rural areas. The source contributions to ultra-fine particle mass PM_0.1 also show clear urban/rural differences. Wood smoke was found to be the major source of PM_0.1 in urban areas while motor vehicle sources were the major contributor of PM_0.1 in rural areas, reflecting the influence from two major highways that transect the Valley.     

Combining Environmental Factors and Agriculturalists’ Observations of Environmental Changes in the Traditional Terrace System of the Amalfi Coast (Southern Italy)

Terraces are traditional engineered ecosystems that affect the hydro-geological equilibrium, slope stability, and local communities. The aims of this paper are (i) identifying environmental factors that affect terrace stability in the Amalfi Coast, (ii) defining agriculturalists’ observations on environmental changes within that system and (iii) exploring potentiality of these observations to better define conservation strategies. All available data on physical and ecological factors recognized to affect the terrace system were collected and analyzed. Interviews were conducted with agriculturalists to obtain long-term observations on environmental factors that interact with this system. Landslides are more frequent where rainfall is high and during winter. Fires have an uneven annual distribution, with higher frequency during summers. Agriculturalists detailed complex interactions among environmental factors, economic elements, and terraces. These observations represent a valuable resource for defining causes and effects of abandonment and for better addressing conservation strategies.

Electronic supplementary material

The online version of this article (doi:10.1007/s13280-013-0433-3) contains supplementary material, which is available to authorized users.     

Spatial and Temporal Variability of Ozone Exposure in Forested Areas of the United States and Canada: 1978—1988

Ambient O₃ exposures have reduced growth rates of tree genotypes in some areas of the United States. For characterizing O₃ exposures in forested areas, data from primarily population-oriented sites have been used. It has been speculated that exposures calculated from population-oriented sites provide estimates greater than those that would actually be experienced in the majority of forested areas. Accordingly, we compared 1988 O₃ data from three remote forested sites with data from several population-oriented monitoring sites in and around the mid? and southern Appalachian Mountains. The number of hours ≥0.08 ppm was lower at the remote forested sites than at the nearby population-oriented locations. In addition, we characterized the temporal variability of O₃ exposures in forested regions of the United States and Canada for the period 1978-1988. We found that the years of highest O₃ exposure in the eastern United States during 1978-1988 were 1978, 1980, 1983, and 1988, with 1988 being the worst year in four of seven eastern forest regions. In 1988, the Whiteface Mountain summit site (1483 m) experienced approximately 10 percent more hourly average concentrations ≥0.08 ppm than in the second highest O₃ exposure year (i.e., 1979). Consistently throughout the 11-year period, the highest O₃ exposures at the Whiteface Mountain site occurred during the late evening and early morning hours, with the result that the longterm 7-h (0900-1559h) exposure index could not distinguish those years in which the highest exposures occurred from those in which the lowest occurred. Similar to the Whiteface Mountain site, two high-elevation Shenandoah National Park sites experienced their highest O₃ exposures in 1988. With the exception of 1986, the lower elevation site (Dickey Ridge) consistently experienced more frequent occurrences of hourly average concentrations ≥0.08 ppm than the higher elevation site (Big Meadows).     

Atmospheric dispersion and transport within coastal regions—Part II. Tracer study of industrial emissions in the California Delta Region

Eight large-scale atmospheric tracer tests, utilizing CBrF₃ and/or SF₆, were conducted during September, 1976, within the California Delta Region. The purpose of this study was to demonstrate the large-scale application of single and double tracer techniques to the study of pollutant transport and dispersion under complex, coastal meteorological conditions.The resulting tracer data base was comprehensive enough to permit accurate mass balances of the tracer; essentially all of the tracer was accounted for by this analysis. On the average, plumes emitted from the Montezuma Hills during the test periods were transported southeast over Stockton into the San Joaquin Valley. As a result of the steady nature of the winds, the commonly used Hino correction was found to grossly underestimate the hourly averaged tracer concentrations computed from 10-s averaged concentrations.Experimentally determined rates of dispersion were greater than those associated with Pasquill-Gifford dispersion curves. In spite of the complex meteorology and terrain, estimates of tracer concentrations based upon the Gaussian plume model were found to be reasonably accurate.The relationship between the horizontal standard deviation of the wind, σ_θ, and the horizontal dispersion parameter of the plume, σ_y, was found to follow σ_y∼-0.85 xσ_θ, where x is the downwind distance of the plume center. Calculated trajectories and arrival times of air parcels based upon a numerical solution to the two-dimensional mass balance equation were found to be in excellent agreement with the tracer data.     

Dioxin/POPs legacy of pesticide production in Hamburg: Part 1—securing of the production area

α-Hexachlorocyclohexane (HCH), β-HCH, and γ-HCH (lindane) were recently included as new persistent organic pollutants (POPs) in the Stockholm Convention. Therefore, the chemicals need to be globally addressed, including the disposal of historic wastes. At most sites, the approximately 85 % of HCH waste isomers were dumped. At a former lindane factory in Hamburg and some other factories the HCH, waste was recycled producing residues with high polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/PCDF) levels. The soil and ground water under the former pesticide factory was/is highly contaminated with HCH (260 tons), chlorobenzenes (550 tons), and PCDD/PCDF (6 kg toxic equivalents (TEQ)). This contamination did not result from disposal operations but from spillages and leakages during the 30 years of the factory's production history. A containment wall has been constructed around the production area to prevent the dispersal of the pollutants. The ground water is managed by a pump and treat system. Over the last 15 years, approximately 10–30 tons of this pollution reservoir has been pumped and incinerated. For the contaminated production buildings, specific assessment and demolition technologies have been applied. In addition to their HCH waste isomer deposition, former lindane/HCH productions need to be assessed for possible recycling practice of HCH and related PCDD/PCDF contamination of the production area and buildings. Since such recycling activities have taken place at several factories in different countries, the experience of assessment and management of the described production area and contaminated buildings could be valuable. Such assessment could be addressed within the frame of the Stockholm Convention.     

Nonparametric factorial analysis of daily weigh-in-motion traffic: implications for the ozone “weekend effect” in Southern California

The Ozone Weekend Effect (OWE) has become increasingly more frequent and widespread in southern California since the mid-1970s. Although a number of hypotheses have been suggested to explain the effect, there remains uncertainty associated with the root factors contributing to elevated weekend ozone concentrations. Targeting the time window of the 1997 Southern California Ozone Study (SCOS97), this paper examines traffic activity data for 14 vehicle classes at 27 weigh-in-motion (WIM) stations in southern California. Nonparametric factorial analyses of light-duty vehicle (LDV) and heavy-duty truck (HDT) traffic volumes indicate significant differences in daily volumes by day of week and between the weekly patterns of daily LDV and HDT volumes. Across WIM stations, the daily LDV volume was highest on Friday and decreased by 10% on weekends compared to that on midweek days. In contrast, daily HDT volumes showed dramatic weekend drops of 53% on Saturday and 64% on Sunday. As a result, LDV to HDT ratios increased by 145% on weekends. Nonparametric tests also suggest that weekly traffic patterns varied significantly between WIM stations located close to (central) and far from (peripheral) the Los Angeles Metro area. Weekend increases in LDV/HDT ratios were more pronounced at central WIM sites due to greater weekend declines of HDT relative to LDV traffic. The implications of these weekly traffic patterns for the OWE in southern California were investigated by estimating daily WIM traffic on-road running exhaust emissions of total organic gas (TOG) and oxides of nitrogen (NO_x) using EMFAC2002 emission factors. The results support the California Air Resource Board's (CARB's) NO_x reduction hypothesis that greater weekend NO_x reductions relative to volatile organic compound (VOC) emissions, in combinations with the VOC-limited ozone system, contribute to the OWE observed in the region. The results from this study can be used to develop weekend on-road mobile emission inventories for the purpose of air quality modeling.     

Ammonia abatement and its impact on emissions of nitrous oxide and methane in Europe—Part 1: method

Agriculture is an important source of NH₃, which contributes to acidification and eutrophication, as well as emissions of the greenhouse gases CH₄ and N₂O. Because of their common sources, emission reduction measures for one of these gases may affect emissions of others. These interrelations are often ignored in policy making. This study presents an analysis of the effects of measures to reduce NH₃ emissions on emissions of N₂O and CH₄ from agriculture in Europe. The analysis combines information from the NH₃ module of the Regional Air pollution INformation and Simulation (RAINS) model for Europe with the IPCC method for national greenhouse gas inventories. The IPCC method for estimating agricultural emissions of N₂O and CH₄ is adjusted in order to use it in combination with the RAINS database for the European agricultural sector. As an example, we applied the adjusted method to the agricultural sector in the Netherlands and found that application of several NH₃ abatement options may result in a substantial increase in N₂O emissions while the effect on CH₄ emissions is relatively small. In Part 2 of this paper we focus on the resulting emissions for all European countries for 1990 and 2010.     

Ozone Air Quality over North America: Part II—An Analysis of Trend Detection and Attribution Techniques

ABSTRACT

Assessment of regulatory programs aimed at improving ambient O₃ air quality is of considerable interest to the scientific community and to policymakers. Trend detection, the identification of statistically significant long-term changes, and attribution, linking change to specific clima-tological and anthropogenic forcings, are instrumental to this assessment. Detection and attribution are difficult because changes in pollutant concentrations of interest to policymakers may be much smaller than natural variations due to weather and climate. In addition, there are considerable differences in reported trends seemingly based on similar statistical methods and databases. Differences arise from the variety of techniques used to reduce nontrend variation in time series, including mitigating the effects of meteorology and the variety of metrics used to track changes. In this paper, we review the trend assessment techniques being used in the air pollution field and discuss their strengths and limitations in discerning and attributing changes in O₃ to emission control policies.     

Spatial heterogeneity of PM10 and O3 in São Paulo, Brazil, and implications for human health studies

Developing exposure estimates is a challenging aspect of investigating the health effects of air pollution. Pollutant levels recorded at centrally located ambient air quality monitors in a community are commonly used as proxies for population exposures. However, if ample intraurban spatial variation in pollutants exists, city-wide averages of concentrations may introduce exposure misclassification. We assessed spatial heterogeneity of particulate matter with an aerodynamic diameter < or = 10 microm (PM10) and ozone (O3) and evaluated implications for epidemiological studies in S?o Paulo, Brazil, using daily (24-hr) and daytime (12-hr) averages and 1-hr daily maximums of pollutant levels recorded at the regulatory monitoring network. Monitor locations were also analyzed with respect to a socioeconomic status index developed by the municipal government. Hourly PM10 and O3 data for the Sāo Paulo Municipality and Metropolitan Region (1999-2006) were used to evaluate heterogeneity by comparing distance between monitors with pollutants' correlations and coefficients of divergence (CODs). Both pollutants showed high correlations across monitoring sites (median = 0.8 for daily averages). CODs across sites averaged 0.20. Distance was a good predictor of CODs for PM10 (p < 0.01) but not O3, whereas distance was a good predictor of correlations for O3 (p < 0.01) but not PM10. High COD values and low temporal correlation indicate a spatially heterogeneous distribution of PM10. Ozone levels were highly correlated (r > or = 0.75), but high CODs suggest that averaging over O3 levels may obscure important spatial variations. Of municipal districts in the highest of five socioeconomic groups, 40% have > or = 1 monitor, whereas districts in the lowest two groups, representing half the population, have no monitors. Results suggest that there is a potential for exposure misclassification based on the available monitoring network and that spatial heterogeneity depends on pollutant metric (e.g., daily average vs. daily 1-hr maximum). A denser monitoring network or alternative exposure methods may be needed for epidemiological research. Findings demonstrate the importance of considering spatial heterogeneity and differential exposure misclassification by subpopulation.