The Southeastern Aerosol Research and Characterization Study,Part 3: Continuous Measurements of Fine Particulate Matter Mass and Composition

Abstract

Deployment of continuous analyzers in the Southeastern Aerosol Research and Characterization Study (SEARCH) network began in 1998 and continues today as new technologies are developed. Measurement of fine particulate matter (PM_2.5) mass is performed using a dried, 30 °C tapered element oscillating microbalance (TEOM). TEOM measurements are complemented by observations of light scattering by nephelometry. Measurements of major constituents include: (1) SO₄ ^2? via reduction to SO₂; (2) NH₄ ⁺ and NO₃ ^? via respective catalytic oxidation and reduction to NO, (3) black carbon (BC) by optical absorption, (4) total carbon by combustion to CO₂, and (5) organic carbon by difference between the latter two measurements. Several illustrative examples of continuous data from the SEARCH network are presented. A distinctive composite annual average diurnal pattern is observed for PM_2.5 mass, nitrate, and BC, likely indicating the influence of traffic-related emissions, growth, and break up of the boundary layer and formation of ammonium nitrate. Examination of PM_2.5 components indicates the need to better understand the continuous composition of the unmeasured “other” category, because it contributes a significant fraction to total mass during periods of high PM_2.5 loading. Selected episodes are presented to illustrate applications of SEARCH data. An SO₂ conversion rate of 0.2%/hr is derived from an observation of a plume from a coal-fired power plant during early spring, and the importance of local, rural sources of NH₃ to the formation of ammonium nitrate in particulate matter (PM) is demonstrated.     

Development of the Ammonia Injection Technology (AIT) for the Control of PCDD/PCDF and Acid Gases from Municipal Solid Waste Incinerators

This article describes the development of the Ammonia Injection Technology (AIT), a technology for the simultaneous control of the emissions of PCDD/PCDF (polychlorinated p-dibenzodioxins and polychlorinated dibenzofurans), HCI, SO₂ and NOX from municipal solid waste incinerators. It briefly reviews the theoretical basis of the technology and the bench-scale and pilot-scale experiments. It describes the results of the pilot-scale experiment in detail and reports on the finding that the formation of PCDD and PCOF takes place in different regions of the boiler system. Finally, a concept is introduced for the treatment of emission control residues which could lead to the recovery of chlorine from waste products and its “recycle” to the chlorine manufacturing process (“closed chlorine life cycle“ concept).     

The Southeastern Aerosol Research and Characterization Study: Part II. Filter-Based Measurements of Fine and Coarse Particulate Matter Mass and Composition

Abstract

The Southeastern Aerosol Research and Characterization Study (SEARCH) was implemented in 1998–1999 to provide data and analyses for the investigation of the sources, chemical speciation, and long-term trends of fine particulate matter (PM_2.5) and coarse particulate matter (PM_10–2.5) in the Southeastern United States. This work is an initial analysis of 5 years (1999–2003) of filter-based PM_2.5 and PM_10–2.5 data from SEARCH. We find that annual PM_2.5 design values were consistently above the National Ambient Air Quality Standards (NAAQS) 15 µg/m³ annual standard only at monitoring sites in the two largest urban areas (Atlanta, GA, and North Birmingham, AL). Other sites in the network had annual design values below the standard, and no site had daily design values above the NAAQS 65 µg/m³ daily standard. Using a particle composition monitor designed specifically for SEARCH, we found that volatilization losses of nitrate, ammonium, and organic carbon must be accounted for to accurately characterize atmospheric particulate matter. In particular, the federal reference method for PM_2.5 underestimates mass by 3–7% as a result of these volatilization losses. Organic matter (OM) and sulfate account for ≥60% of PM_2.5 mass at SEARCH sites, whereas major metal oxides (MMO) and unidentified components (“other”) account for ≥80% of PM_10–2.5 mass. Limited data suggest that much of the unidentified mass in PM_10–2.5 may be OM. For paired comparisons of urban-rural sites, differences in PM_2.5 mass are explained, in large part, by higher OM and black carbon at the urban site. For PM₁₀, higher urban concentrations are explained by higher MMO and “other.” Annual means for PM_2.5 and PM_10–2.5 mass and major components demonstrate substantial declines at all of the SEARCH sites over the 1999–2003 period (10–20% in the case of PM_2.5, dominated by 14–20% declines in sulfate and 11–26% declines in OM, and 14–25% in the case of PM_10–2.5, dominated by 17–30% declines in MMO and 14–31% declines in “ other”). Although declining national emissions of sulfur dioxide and anthropogenic carbon may account for a portion of the observed declines, additional investigation will be necessary to establish a quantitative assessment, especially regarding trends in local and regional emissions, primary carbon emissions, and meteorology.     

Biodegradation kinetics and toxicity of vegetable oil triacylglycerols under aerobic conditions

The aerobic biodegradation of five triacylglycerols (TAGs), three liquids [triolein (OOO), trilinolein (LLL), and trilinolenin (LnLnLn)] and two solids [tripalmitin (PPP) and tristearin (SSS)] was studied in water. Respirometry tests were designed and conducted to determine the biochemical oxygen demand (BOD) parameters of the compounds. In the case of the solid lipids, the degradation process was limited by their extremely non-polar nature. When added to water, PPP and SSS formed irregular clumps or gumballs, not a fine and uniform suspension required for the lipase activity. After 30 days, appreciable mineralization was not achieved; therefore, first-order biodegradation coefficients could not be determined. The bioavailability of the liquid TAGs was restricted due to the presence of double bonds in the fatty acids (FAs). An autoxidation process occurred in the allylic chains, resulting in the production of hydroperoxides. These compounds polymerized and became non-biodegradable. Nevertheless, the non-oxidized fractions were readily mineralized, and BOD rate constants were estimated by non-linear regression: LLL (k = 0.0061 h⁻¹) and LnLnLn (k = 0.0071 h⁻¹) were degraded more rapidly than OOO (k = 0.0025 h⁻¹). Lipids strongly partitioned to the biomass and, therefore, Microtox^® toxicity was not observed in the water column. However, EC₅₀ values (<15% sample volume) were measured in the solid phase.     

Age dependent acute oral toxicity of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and two anaerobic N-nitroso metabolites in deer mice (Peromyscus maniculatus)

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) transforms anaerobically into N-nitroso compounds: hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine (MNX), hexahydro-1,3-dinitroso-5-nitro-1,3,5-triazine (DNX), and hexahydro-1,3,5-trinitroso-1,3,5-triazine (TNX). Exposure to these N-nitroso metabolites may occur in areas contaminated with explosives, as anaerobic degradation occurs via some bacteria and is one remediation strategy used for RDX. Few papers report acute oral toxicity and none have evaluated age dependent toxicity of RDX or its N-nitroso metabolites. Median lethal dose (LD₅₀) was determined in deer mice (Peromyscus maniculatus) of three age classifications 21 d, 50 d, and 200 d for RDX, MNX, and TNX using the US EPA up-and-down procedure (UDP). Hexahydro-1,3,5-trinitro-1,3,5-triazine and N-nitroso metabolites caused similar overt signs of toxicity. Median lethal dose for 21 d deer mice were 136, 181, and 338 mg/kg for RDX, MNX, and TNX, respectively. Median lethal dose for 50 d deer mice were 319, 575, and 338 mg/kg for RDX, MNX, and TNX, respectively. Median lethal dose for 200 d deer mice were 158, 542, and 999 mg/kg for RDX, MNX, and TNX, respectively. These data suggest that RDX is the most potent compound tested, and age dependent toxicity may exist for all compounds and could play a role in RDX and RDX N-nitroso metabolite ecological risk evaluation of terrestrial wildlife at RDX contaminated sites.     

Fate of sex hormones in two pilot-scale municipal wastewater treatment plants: conventional treatment

The fate of seven sex hormones (estrone (E1), estradiol (E2), estriol (E3), ethinylestradiol (EE2), testosterone, androstenedione, and progesterone) was determined in two pilot-scale wastewater treatment plants operated under conventional loading conditions. The levels of hormones in both the liquid and the solid matrixes of the plants were determined. Each of the two 20-l/h pilot-scale plants consisted of a primary clarifier followed by a three-stage aeration tank and a final clarifier. The primary sludge and the waste activated sludge (WAS) were digested anaerobically in one pilot plant and aerobically in the other. The pilot plants were fed a complex synthetic wastewater spiked with the hormones. Levels of testosterone, androstenedione and progesterone were close to method detection limit (MDL) concentrations in the final and digester effluents (both liquid and solid phases) and were considered as completely removed. Average mass flux removals from the liquid streams (plant influent minus secondary clarifier effluent) for the natural estrogens were 82% for E1, 99% for E2, and 89% for (E1+E2). An average overall removal of only 42% was achieved for EE2. These values reflect removals averaged for the two pilot plants.     

Oily wastewater treatment using a novel hybrid PBR-UASB system

In this study, anaerobic treatability of oily wastewater was investigated in a hybrid reactor system consisting of a packed bed reactor (PBR) followed by an upflow anaerobic sludge blanket (UASB) reactor at 35 degrees C. The system was operated using real pet food wastewater at different hydraulic retention times and loading rates for 165 d. The PBR was packed with sol-gel/alginate beads containing immobilized enzyme which hydrolyzed the oil and grease (O&G) into free long chain fatty acids, that were biodegraded by the UASB. The hybrid system was operated up to an oil loading rate of 4.9 kg O&Gm(-3)d(-1) (to the PBR) without any operational problems for a period of 100 d, with COD and O&G removal efficiencies above 90% and no sludge flotation was observed in the UASB. Beads supplement to the PBR was less than 2 g d(-1) and the relative activity was about 70%. Further increment in O&G loading to 18.7 kg O&Gm(-3)d(-1) caused destabilization of the system with 0.35% (v float/v feed) sludge float removed from the UASB.     

Derivation of ozone flux-yield relationships for lettuce: a key horticultural crop

Ozone flux-response relationships were derived for lettuce, employing a multiplicative approach to model the manner in which stomatal conductance is influenced by key environmental variables, using a dataset collected during field experimentation in Crete and yield-response relationships derived from parallel open-top chamber experiments. Regional agronomic practices were adopted throughout. Computed versus measured data revealed that the derived model explained 51% (P<0.001) of the observed variation in stomatal conductance. Concentration-based indices were compared with flux-based indices. Analyses revealed a significant relationship between accumulated stomatal ozone flux and yield employing flux threshold cut-offs up to 4 nmol m(-2) s(-1). Regressions employing very low or zero flux thresholds resulted in the strongest yield-flux relationships (explaining approximately 80% (P<0.05) of the variation in the dataset).     

In vitro assessment of the effects of cadmium and zinc on mammalian nerve fibres

Zinc and cadmium are environmental contaminants that have a wide range of effects on the nervous system, but zinc is also considered to be an important metal in the human body. In this study the effect of CdCl(2) and ZnCl(2), at concentrations of 50,150, 250 and 500 microM, on the nerve fibres of the sciatic nerve of the rat isolated in a three-chamber recording bath were studied. At the same concentrations, CdCl(2) and ZnCl(2) were found to have almost the same inhibitory effect on the compound action potential (CAP) of the nerve fibres. Their concentration-effect curves almost overlap and there was no significant difference in their EC(50) which for CdCl(2) is 250.1+/-18 microM (n=5) and for ZnCl(2) is 282.2+/-25 microM (n=5) correspondingly (P>0.05). The no-observed-effect concentration (NOEC) was estimated to be 50-100 microM for both metals. The identical inhibitory effect of both metals on the sciatic nerve fibres indicates a common mode of action which is related to their potential to generate reactive oxygen species (ROS).