The Southeastern Aerosol Research and Characterization Study: part 1--Overview

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.     

Comparative assessment of municipal wastewater disposal methods in southeast Florida.

A comparative assessment of the risks of three effluent disposal alternatives currently available to wastewater utilities in Southeast Florida is presented in this paper. The alternatives are: deep well injection and ocean outfalls following secondary treatment, and surface water (canal) discharges following secondary wastewater treatment, filtration and nutrient removal. Water quality data, relative to disposal of wastewater treatment plant effluent were gathered, along with water quality data on the receiving waters, from utilities. Comparisons and conclusions regarding potential health concerns associated with the three disposal alternatives are presented. The results indicated that health risks associated with deep wells were generally lower than those of the other two alternatives. The proximity of injection wells to aquifer storage and recovery wells was a determining factor relative to injection well risk. Urban ecological risks were also indicated to be lower, though impacts of urban water use/reuse to the Everglades were not studied. Additional data collection and analysis were recommended to understand the effects of wastewater management on the cycling of water, nutrients and other constituents on southeast Florida. In particular, it was recommended that monitoring of effluents for nitrosamines and pharmaceutically active substances be implemented on a broad scale.     

The midlatitude North American background aerosol and global aerosol variation

Protocols for the particulate matter (PM) National Ambient Air Quality Standards (NAAQS), and the Regional Haze Rule (RHR) give two complementary definitions for "natural" background airborne particle concentrations in the United States. The definition for the NAAQS derives largely from reported annual averages, whereas the definition for the RHR takes into account the frequency of occurrence of a range of visibility conditions estimated using fine particle composition. These definitions are simple, static representations of background or "unmanageable" aerosol conditions in the United States. An accumulation of data from rural-remote sites representing global conditions indicates that the airborne particle concentrations are highly variable. Observational campaigns show weather-related variations, including incidents of regional or intercontinental transport of pollution that influence background aerosol levels over midlatitude North America. Defining a background in North America based on long-term observations relies mainly on the remote-rural IMPROVE network in the United States, with a few additional measurements from Canada. Examination of the frequency of occurrence of mass concentrations and particle components provides insight not only about annual median conditions but also the variability of apparent background conditions. The results of this analysis suggest that a more elaborate approach to defining an unmanageable background could improve the present approach taken for information input into the U.S. regulatory process. An approach interpreting the continental gradients in fine PM (PM2.5) concentrations and composition may be warranted.     

Kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE)

The kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE) in aqueous solutions at various pH, temperature, oxidant concentration and ionic strength levels was studied. The MTBE degradation was found to follow a pseudo-first-order decay model. The pseudo-first-order rate constants of MTBE degradation by persulfate (31.5 mM) at pH 7.0 and ionic strength 0.11 M are approximately 0.13 x 10(-4), 0.48 x 10(-4), 2.4 x 10(-4) and 5.8 x 10(-4) S(-1) at 20, 30, 40 and 50 degrees C, respectively. Under the above reaction conditions, the reaction has an activation energy of 24.5 +/- 1.6 kcal/ mol and is influenced by temperature, oxidant concentration, pH and ionic strength. Raising the reaction temperature and persulfate concentration may significantly accelerate the MTBE degradation. However, increasing both pH (over the range of 2.5-11) and ionic strength (over the range of 0.11-0.53 M) will decrease the reaction rate. Reaction intermediates including tert-butyl formate, tert-butyl alcohol, acetone and methyl acetate were observed. These intermediate compounds were also degraded by persulfate under the experimental conditions. Additionally, MTBE degradation by persulfate in a groundwater was much slower than in phosphate-buffer solutions, most likely due to the presence of bicarbonate ions (radical scavengers) in the groundwater.     

Development and demonstration of an explicit lumped-parameter biofilter model and design equation incorporating monod kinetics

Biofiltration is an economical air pollution control (APC) technology, particularly suitable for the treatment of air-streams having high flow rates and low concentrations of volatile organic compounds (VOCs). This technology utilizes enzymatic catalysis at ambient conditions to mineralize such pollutants to CO2, H2O, and salts. A pilot-scale study conducted for more than 4 years investigated the development of a new biofiltration technology employing trickle bed air biofilters (TBABs). Following the completion of this experimental study, additional data analysis was performed to develop a simple lumped-parameter biofilter model, assuming first-order kinetics. This model related the observed biofilter performance to the principle independent physical, thermodynamic, and biochemical parameters. The initial model has subsequently been expanded to incorporate Monod kinetics. In this paper, the development and use of the final explicit lumped-parameter biofilter model and design equation, incorporating Monod kinetics, are presented. To facilitate the application of this model, practical procedures are also presented for the determination of VOC solubility, VOC biokinetic Monod parameters, and the maximum practical biofilter inlet VOC concentration.     

Ozone patterns for three metropolitan statistical areas in North Carolina, USA

As part of an effort by the state of North Carolina to develop a State Implementation Plan (SIP) for 1-h peak ozone control, a network of ozone stations was established to monitor surface ozone concentrations across the state. Between 19 and 23 ozone stations made continuous surface measurements between 1993 and 1995 surrounding three major metropolitan statistical areas (MSAs): Raleigh/Durham (RDU), Charlotte/Mecklenburg (CLT), and Greensboro/High Point/Winston-Salem (GSO). Statistical averages of the meteorological and ozone data were performed at each Metropolitan Statistical Area (MSA) to study trends and/or relationships on high ozone days (days in which one of the MSA sites measured an hourly ozone concentration90.0 ppbv). County emission maps of precursor gases, wind roses, total area averages of ozone, total downwind averages of ozone deviations, upwind averages of ozone, and a modified delta ozone analysis were all obtained and analyzed. The results of this study show a reduction in the delta ozone relative to an earlier study at RDU, but no average significant change at CLT (no comparison can be made for GSO). The statistical data analyses in this study are used to quantify the importance of local contributions and regional transport, to ozone air pollution in the MSAs.     

Natural products: seasonal variation in trichome counts and contents in Lycopersicum hirsutum f. glabratum

Wild tomato leaves possess a pest-resistance mechanism in their glandular trichomes and the exudates they produce. Type IV and VI glandular trichomes on the leaves of five wild tomato accessions of Lycopersicum hirsutum f. glabratum (PI 126449, PI 134417, PI 134418, PI 251304, and LA 407) grown under greenhouse conditions were counted. Major chemical compounds from glandular leaf trichomes of the accessions tested were extracted, purified, and quantified at different periods during the growing seasons by gas chromatography (GC) and mass spectrometry (GC/MS). The toxicity of two methylketones (2-undecanone and 2-tridecanone), the major constituents of the accessions tested, to adults of the sweetpotato whitefly, Bemisia tabaci (Gennadius) and fourth instar larvae of the Colorado potato beetle (CPB), Leptinotarsa decemlineata (Say), was determined using no-choice bioassays. 2-undecanone caused 80% mortality of the fourth instar larvae of the CPB at the highest concentration tested (100 mg 2-undecanone mL(-1) of acetone) while 2-tridecanone caused 72% mortality of whiteflies at 20 mg 2-tridecanone mL(-1) of 65% ethanol. The concentration of 2-undecanone and 2-tridecanone on the leaves of each of the five accessions of L. hirsutum f. glabratum and the mass spectra of 2-undecanone and 2-tridecanone are presented. Overall, the concentration of 2-undecanone on the leaves was significantly higher than 2-tridecanone. Concentration of the two methylketones varied among accessions and sampling season. Plants produced the highest concentration of 2-undecanone during the month of August. On average, each plant of accession PI 251304 provided 354 g fresh leaves (averaging about 52,353 cm2 exposed leaf surface area) and produced 32.5 and 8.7 mg of 2-undecanone and 2-tridecanone, respectively. L. hirsutum f. glabratum accessions may become a valuable source of natural products, which could minimize reliance on synthetic pesticides.     

Spatial inhomogeneity in pollutant concentrations, and their implications for air quality model evaluation

The Southern California Air Quality Study database provides a valuable resource with which to test urban-scale photochemical models and to achieve a better understanding of the atmospheric dynamics of pollutant formation. The CIT model was evaluated using the SCAQS database according to traditional model performance guidelines. A first application, reported previously, focused on model enhancement and application of the model to the 27–29 August 1987 episode. This study evaluates the CIT model using the 24–25 June SCAQS episode, providing further evaluation of the model. Results show that the CIT airshed model can follow the diurnal variations of reactive species and the transport for relatively unreactive species. The normalized gross error for ozone was 31 % in June compared to 38% in August. However, to fully judge model performance in proper perspective, a question arises: “How well do the measurements reflect the air quality surrounding the monitoring station, not just in that location?” This is an important but seldom quantitatively considered factor, not only in model evaluation but in the study of health effects as well. Analyses indicate that individual concentration measurements only approximately represent the true volume-averaged concentrations within a computational grid cell and that significant spatial variations exist. Thus any evaluation of models using these data sets should take these local variations into consideration. A series of tests found that the local inhomogeneities had a normalized gross error in the range of 25–45% depending on the pollutant. In this context, the performance of the CIT model is consistent with known modeling limitations such as emissions inventories and sub-grid scale variation of observations.     

Assessing the recovery of lakes in southeastern Canada from the effects of acidic deposition

Reductions in North American sulfur dioxide (SO2) emissions promoted expectations that aquatic ecosystems in southeastern Canada would soon recover from acidification. Only lakes located near smelters that have dramatically reduced emissions approach this expectation. Lakes in the Atlantic provinces, Quebec and Ontario affected only by long-range sources show a general decline in sulfate (SO4(2-)) concentrations, but with a relatively smaller compensating increase in pH or alkalinity. Several factors may contribute to the constrained (or most likely delayed) acidity response: declining base cation concentrations, drought-induced mobilization of SO4(2-), damaged internal alkalinity generation mechanisms, and perhaps increasing nitrate or organic anion levels. Monitoring to detect biological recovery in southeastern Canada is extremely limited, but where it occurs, there is little evidence of recovery outside of the Sudbury/Killarney area. Both the occurrence of Atlantic salmon in Nova Scotia rivers and the breeding success of Common Loons in Ontario lakes are in fact declining although factors beyond acidification also play a role. Chemical and biological models predict that much greater SO2 emission reductions than those presently required by legislation will be needed to promote widespread chemical and latterly, biological recovery. It may be unrealistic to expect that pre-industrial chemical and biological conditions can ever be reestablished in many lakes of southeastern Canada.