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.     

Ozone Air Quality over North America: Part I—A Review of Reported Trends

ABSTRACT

Ozone and precursor trends can be used to measure the effectiveness of regulatory programs that have been implemented. In this paper, we review trends in the concentrations of O₃, NO_x, and HCs over North America that have been reported in the literature. Although most existing trend studies are confounded by meteorological variability, both the raw data trends and the trends adjusted for meteorology collectively indicate a general decreasing trend in O concentrations in most areas of the United States during 1985-1996. In Canada, mean daily maximum 1-hr O₃ concentrations at urban sites show mixed trends with a majority of sites showing an increase from 1980 to 1993. Mean daily maximum 1-hr O₃ at most regionally representative Canadian sites appears to decrease from 1985 to 1993 or shows no significant change. There are far fewer data and analyses of NO_x and HC trends. Available studies covering various ranges of years indicate decreases in ambient NO_x and HC concentrations in Los Angeles, CA, decreases in HC concentrations in northeastern U.S. cities, and decreases in NO concentrations in Canadian cities. Two key needs are long-term HC and NO_x measurements, particularly at rural sites, and a systematic comparison of trend detection techniques on a reference data set.     

Air Quality Criteria—Toxicological Appraisal for Oxidants,Nitrogen Oxides,and Hydrocarbons

The ultimate aim of toxicological studies is to determine the effects of pollutants on the health and welfare of human beings. To get this it is essential to conduct animal studies to evaluate the potential toxicity of different pollutants. Toxicological appraisal of the photochemical oxidant type of air pollution shows: (1) The effects are primarily on the lungs and the senses. (2) There is impairment of pulmonary function in humans at concentrations found in polluted air. (3) Both ozone and nitrogen dioxide tend to oxidize in animals the lung tissue for a time. This process creates agents which have the potential for cross-linking structural proteins, and this process initiates inflammation which accelerates cell turnover rates. Both crosslinking and cell turnover rates are factors in aging, which may thus be accelerated by years of repeated exposure to oxidants. (4) Long-term exposure to low levels of nitrogen dioxide can produce pre-emphasematous lesions in the lungs of rats and mice. Studies with other species are needed. (5) Ozone, nitrogen dioxide, and dilute irradiated car exhausts increase susceptibility to respiratory infection.

The constant search for more sophisticated and sensitive techniques to detect subtle changes indicative of pre-disease conditions should not be relaxed. Such techniques will provide chronic disease predictors of great relevance as air quality criteria.     

Polyfunctional Plants for Industrial Waste Disposal—Part II: Economics and Model Evaluation

ABSTRACT

This is the second part of a two-part paper dealing with the preliminary design and costing of polyfunctional waste treatment plants. In this article, we present some criteria for estimating capital investment and annual operating costs of polyfunctional plants for industrial waste treatment. The process and equipment design methods presented in Part I of this article, together with the economic approach proposed here, allow for complete technical/economic analyses. The overall mathematical model appears to be a useful tool in economic feasibility studies. The accuracy of the developed computer mathematical model has been demonstrated, referring to actual cost data from the literature.     

Aerosol Research and Inhalation Epidemiological Study (ARIES): Air Quality and Daily Mortality Statistical Modeling— Interim Results

ABSTRACT

The Aerosol Research and Inhalation Epidemiological Study (ARIES) is an EPRI-sponsored project to collect air quality and meteorological data at a single site in northwestern Atlanta, GA. Seventy high-resolution air quality indicators (AQIs) are used to examine statistical relationships between air quality and health outcome end points. Contemporaneous mortality data are collected for Fulton and DeKalb counties in Georgia. Currently, 12 months of air quality and weather data are available for analysis, from August 1998 through July 1999.

The interim mortality analysis used Poisson regression in generalized additive models (GAMs). The estimated log-linear association of mortality with various AQIs was adjusted for smoothed functions of time and meteorological data. The analysis considered daily deaths due to all nonaccidental causes, deaths to persons 65 years or older, and deaths in each of the two constituent counties. The fine particle effect associated with the four mortality subgroups, using only today (lag 0), yesterday (lag 1), 2-day average (average of today and yesterday), and first difference (today minus yesterday) measurements of the air quality relative to today's number of deaths was positive for lag 0, lag 1, and 2-day average and positive only for decedents at least 65 years of age using first difference. The t values ranged from 0.81 to 1.15 for lag 0, 1.04 to 1.53 for lag 1, 1.10 to 1.66 for 2-day average, and -0.32 to 0.33 for first difference with 346 or 347 days of data. No statistically significant estimate of the linear coefficient was found for the other 14 air quality variables in our interim analysis for the four mortality subgroups. We discuss diagnostics to support these models.

These interim analyses did not include an evaluation of sensitivity to a larger set of lag structures, nonlinear model specifications, multipollutant analyses, alternative weather model and smoothing model specifications, air pollution imputation schemes, or cause-specific mortality indicators, nor did they include a full reporting of model selection or goodness-of-fit indicators. No conclusion can be drawn at this time about whether the findings from subsequent studies have sufficiently greater power to detect effects comparable to those found in other U.S. cities including at least 2 or 3 years of data.     

N-alkane studies in the troposphere—II: Gas and particulate concentrations in Indian Ocean air

Westerly winds arriving at the Australian Clean Air Baseline Station Cape Grim at the North Western tip of Tasmania have exceedingly long trajectories over the Indian Ocean. In these air masses we found the n-alkanes C₉-C₂₈ to be always present in the gas phase and also in the aerosols. In aerosols we also measured total organic matter and its general composition. All these concentrations agree fairly well with our earlier data in marine air over the North Atlantic Ocean. Calculations of the life time of the gas phase n-alkanes due to reaction with OH radicals lead to the conclusion that these n-alkanes must be of oceanic origin in Indian Ocean air and — to a large extent — also in the North Atlantic air. The same conclusion is reached for the organic component in aerosols. Water Analyses show that the n-alkanes C₉-C₂₈ seem to be normal constituents of the oceans.     

An Air Quality Data Analysis System for Interrelating Effects,Standards, and Needed Source Reductions: Part 13— Applying the EPA Proposed Guidelines for Carcinogen Risk Assessment to a Set of Asbestos Lung Cancer Mortality Data

Abstract

The Clean Air Act Amendments of 1990 (CAAA-90) list 189 hazardous air pollutants (HAPs) for which “safe” ambient concentrations are to be determined. The primary purpose of this paper is to develop two mathematical models, lognormal and logarithmic, that effectively express excess lung cancer mortality as a function of asbestos concentration for an example set of data and also to suggest using these two models for additional HAPs. The secondary purpose of this paper is to calculate a “safe” asbestos concentration by first assuming a default linear extrapolation (to one excess death per million people, as specified for carcinogenic HAPs). The resulting “safe” concentration is an impossible-to-achieve 1/1000 of present background asbestos concentrations. A letter to the editor and a response in this Journal issue use additional asbestos data that suggest that the “safe” concentration should be about 730 times higher than first calculated here and that a default nonlinear extrapolation should be used instead, with the “safe” concentration proportional to the desired mortality level raised to the 0.39 power. These results suggest that the most important problem in setting a “safe” concentration for each carcinogenic HAP is to determine the correct nonlinear extrapolation to use for each HAP.     

Characterization of PM25 and PM10 in the South Coast Air Basin of Southern California: Part 1—Spatial Variations

ABSTRACT

In December 1994, the South Coast Air Quality Management District (SCAQMD) initiated a comprehensive program, the PM₁₀ Technical Enhancement Program (PTEP), to characterize fine PM in the South Coast Air Basin (SCAB). A 1-year special particulate monitoring project was conducted from January 1995 to February 1996 as part of the PTEP. Under this enhanced monitoring, HNO₃, NH₃, and speciated PM₁₀ and PM_2.5 concentrations were measured at five stations (Anaheim, downtown Los Angeles, Diamond Bar, Fontana, and Rubidoux) in the SCAB and at one background station at San Nicolas Island. PM_2.5 and PM₁₀ mass and 43 individual species were analyzed for a full chemical speciation of the particle data. The PTEP data indicate that the most abundant chemical components of PM₁₀ and PM₂₅ in the SCAB are NH₄+ (8-9% of PM₁₀ and 14-17% of PM₂₅), NO₃ ^- (23-26% of PM₁₀ and 28-41% of PM₂₅), SO₄= (6-11% of PM₁₀ and 9-18% of PM_{2 5}), organic carbon (OC) (15-19% of PM₁₀ and 18-26% of PM_2.5), and elemental carbon (EC) (5-8% of PM₁₀ and 8-13% of PM₂₅). On an annual average basis, PM₂₅ comprises 52-59% of the SCAB PM₁₀. Annual average PM₁₀ and PM_2.5 concentrations showed strong spatial variations, low at coastal sites and high at inland sites. Annual average PM₁₀ concentrations varied from 40.8 ug/m³ at Anaheim to 76.8 ug/m³ at Rubidoux, while annual average PM_2.5 concentrations varied from 21.7 ug/m³ at Anaheim to 39.8 ug/m³ at Rubidoux. The chemical characterizations of the PM_2.5 and PM₁₀ concentrations, as well as their spatial variations, were examined; the important findings are summarized in this paper, and the temporal variations are discussed in the companion paper.¹     

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.     

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.     

Determination of Atmospheric Nitrogen Input to Lake Greenwood,South Carolina: Part 2—Gaseous Measurements and Modeling

Abstract

The Reedy River branch of Lake Greenwood, SC, has repeatedly experienced summertime algal blooms, upsetting the natural system. A series of experiments were carried out to investigate atmospheric nitrogen (N) input into the lake. N was examined because of the insignificant phosphorus dry atmospheric flux and the unique nutrient demands of the dominant algae (Pithophora oedogonia) contributing to the blooms. Episodic atmospheric measurements during January and March 2001 have shown that the dry N flux onto the lake ranged from 0.9 to 17.4 kg N/ha-yr, and on average is caused by nitric acid (HNO₃; 31%), followed by nitrogen dioxide (NO₂; 23%), fine ammonium (NH₄ ⁺; 20%), coarse nitrate (NO₃ ^?; 16%), fine NO₃ ⁺ (5%), and coarse NH₄ ⁺ (5%). Similar measurements in Greenville, SC (the upper watershed of the Reedy River), showed that the dry N deposition flux there ranged from 1.4 to 9.7 kg N/ha-yr and was mostly caused by gaseous deposition (40% NO₂ and 40% HNO₃). The magnitude of this dry N deposition flux is comparable to wet N flux as well as other point sources in the area. Thermodynamic modeling showed low concentrations of ammonia, relative to the particulate NH₄ ⁺ concentrations.     

A History of the Production and Use of Carbon Tetrachloride,Tetrachloroethylene, Trichloroethylene and 1,1,1-Trichloroethane in the United States: Part 2—Trichloroethylene and 1,1,1-Trichloroethane

Carbon tetrachloride (CTC), tetrachloroethylene (PCE), trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA) were four of the most widely used cleaning and degreasing solvents in the United States. Part 2 of this article describes the history of TCE and TCA. TCE production in the United States began in the early 1920s. TCE was used as a replacement for petroleum distillates in the dry-cleaning industry, and became the solvent of choice for vapor degreasing in the 1930s. TCE’s use as a degreaser decreased in the 1960s due to toxicity concerns and the increasing popularity of TCA. Significant TCA use began in the 1950s with the development of suitable stabilizer formulations. In the 1990s, TCA was phased out under the Montreal Protocol due to its role in stratospheric ozone depletion.     

Light Scattering Characteristics of Aerosols at Ambient and as a Function of Relative Humidity: Part II—A Comparison of Measured Scattering and Aerosol Concentrations Using Statistical Models

ABSTRACT

The eastern United States national parks experience some of the worst visibility conditions in the nation. To study these conditions, the Southeastern Aerosol and Visibility Study (SEAVS) was undertaken to characterize the size-dependent composition, thermodynamic properties, and optical characteristics of the ambient atmospheric particles. It is a cooperative three-year study that is sponsored by the National Park Service and the Electric Power Research Institute and its member utilities. The field portion of the study was carried out from July 15 to August 25, 1995.

The study design, instrumental configuration, and estimation of aerosol types from particle measurements is presented in a companion paper. In the companion paper, we compare measurements of scattering at ambient conditions and as functions of relative humidity to theoretical predictions of scattering. In this paper, we make similar comparisons, but using statistical techniques. Statistically derived specific scattering associated with sulfates suggest that a reasonable estimate of sulfate scattering can be arrived at by assuming nominal dry specific scattering and treating the aerosols as an external mixture with ammoniation of sulfate accounted for and by the use of Tang's growth curves to predict water absorption. However, the regressions suggest that the sulfate scattering may be underestimated by about 10%. Regression coefficients on organics, to within the statistical uncertainty of the model, suggest that a reasonable estimate of organic scattering is about 4.0 m²/g.

A new analysis technique is presented, which does not rely on comparing measured to model estimates of scattering to evoke an understanding of ambient aerosol growth properties, but rather relies on measurements of scattering as a function of relative humidity to develop actual estimates of f(RH) curves. The estimates of the study average f(RH) curve for sulfates compares favorably with the theoretical f(RH) curve for ammonium bisulfate, which is in turn consistent with the study average sulfate am-moniation corresponding to a molar ratio of NH₄/SO₄ of approximately one. The f(RH) curve for organics is not significantly different from one, suggesting that organics are weakly to nonhygroscopic.     

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.     

A History of the Production and Use of Carbon Tetrachloride,Tetrachloroethylene, Trichloroethylene and 1,1,1-Trichloroethane in the United States: Part 1—Historical Background; Carbon Tetrachloride and Tetrachloroethylene

Carbon tetrachloride (CTC), tetrachloroethylene (PCE), trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA) were four of the most widely used cleaning and degreasing solvents in the United States. These compounds were also used in a wide variety of other applications. The history of the production and use of these four compounds is linked to the development and growth of the United States' synthetic organic chemical industry, and historical events that affected the development and use of chlorinated solvents in general. Part 1 of this article includes a discussion of the historical background common to each of the four solvents, followed by discussion on the history of CTC and PCE. In the early years of the 20th century, CTC became the first of the four solvents to come into widespread use. CTC was used as a replacement for petroleum distillates in the dry-cleaning industry, but was later replaced by PCE. In the 1990s, CTC was phased out under the Montreal Protocol due to its role in stratospheric ozone depletion.     

A Vehicle Emissions System Using a Car Simulator and a Geographical Information System: Part 1—System Description and Testing

Abstract

A methodology for estimating vehicular emissions comprising a car simulator, a basic traffic model, and a geographical information system is capable of estimating vehicle emissions with high time and space resolution. Because of the extent of the work conducted, this article comprises two sections: In Part 1 of this work, we describe the system and its components and use examples for testing it. In Part 2 we will study in more detail the emissions of the sample fleet using the system and will make comparisons with another emission model. The experimental data for the car simulator is obtained using on-board measuring equipment and laboratory Fourier transform IR (FTIR) measurements with a dynamometer following typical driving cycles. The car simulator uses this data to generate emission factors every second. These emission factors, together with information on car activity and velocity profiles of highways and residential and arterial roads in Mexico City in conjunction with a basic traffic model, provide emissions per second of a sample fleet. A geographical information system is used to localize these road emissions.     

Agricultural solid waste for sorption of metal ions: part I—characterization and use of lettuce roots and sugarcane bagasse for Cu(II), Fe(II), Zn(II), and Mn(II) sorption from aqueous medium

Sugarcane bagasse and hydroponic lettuce roots were used as biosorbents for Cu(II), Fe(II), Zn(II), and Mn(II) removal from monoelemental solutions in aqueous medium, at pH 5.5, using batch procedures. These biomasses were studied in natura (lettuce roots, NLR, and sugarcane bagasse, NSB) and modified with HNO₃ (lettuce roots, MLR, and sugarcane bagasse, MSB). Langmuir, Freundlich, and Dubinin-Radushkevich non-linear isotherm models were used to evaluate the data from the metal ion adsorption assessment. The maximum adsorption capacities (q_max) in monoelemental solution, calculated using the Langmuir isothermal model for Cu(II), Fe(II), Zn(II), and Mn(II), were respectively 24.61, 2.64, 23.04, and 5.92 mg/g for NLR; 2.29, 16.89, 1.97, and 2.88 mg/g for MLR; 0.81, 0.06, 0.83, and 0.46 mg/g for NSB; and 1.35, 2.89, 20.76, and 1.56 mg/g for MSB. The Freundlich n parameter indicated that the adsorption process was favorable for Cu(II) uptake by NLR; Fe(II) retention by MLR and MSB; and Zn(II) sorption by NSB, MLR, and NSB and favorable for all biomasses in the accumulation of Mn(II). The Dubinin-Radushkevich isotherm was applied to estimate the energy (E) and type of adsorption process involved, which was found to be a physical one between analytes and adsorbents. Organic groups such as O–H, C–O–C, CH, and C=O were found in the characterization of the biomass by FTIR. In the determination of the biomass surface charges by using blue methylene and red amaranth dyes, there was a predominance of negative charges.