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.     

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.     

Synthesis of the two minor isomers, delta- and epsilon-1,2,5,6,9,10-hexabromocyclododecane, present in commercial hexabromocyclododecane

Hexabromocyclododecane (HBCD) is prepared commercially by bromination of cis,trans,trans-cyclododecatriene (ctt-CDT) and widely used as a flame retardant, particularly in polystyrene foams. Commercial HBCD consists largely of three diastereomers, alpha-, beta-, and gamma-HBCD, the structures of which have been known for many years. Recently, the presence in the mixture of small amounts of two minor diastereomers, delta- and epsilon-HBCD, has been reported. Bearing in mind the manner in which commercial HBCD is generated, it was anticipated that these components are probably formed by bromination of trans,trans,trans-cyclododecatriene (ttt-CDT), a common contaminant in commercial ctt-CDT. Indeed, when a sample of ttt-CDT was brominated it gave two products, the NMR spectra and LC/MS and GC/MS behaviour of which confirmed that they are identical to the minor components, delta- and epsilon-HBCD, present in commercial HBCD.     

Sensitivity analysis and evaluation of MicroFacPM: a microscale motor vehicle emission factor model for particulate matter emissions

A microscale emission factor model (MicroFacPM) for predicting real-time site-specific motor vehicle particulate matter emissions was presented in the companion paper titled "Development of a Microscale Emission Factor Model for Particulate Matter (MicroFacPM) for Predicting Real-Time Motor Vehicle Emissions". The emission rates discussed are in mass per unit distance with the model providing estimates of fine particulate matter (PM2.5) and coarse particulate matter. This paper complements the companion paper by presenting a sensitivity analysis of the model to input variables and evaluation model outputs using data from limited field studies. The sensitivity analysis has shown that MicroFacPM emission estimates are very sensitive to vehicle fleet composition, speed, and the percentage of high-emitting vehicles. The vehicle fleet composition can affect fleet emission rates from 8 mg/mi to 1215 mg/mi; an increase of 5% in the smoking (high-emitting) current average U.S. light-duty vehicle fleet (compared with 0%) increased PM2.5 emission rates by -272% for 2000; and for the current U.S. fleet, PM2.5 emission rates are reduced by a factor of -0.64 for speeds >50 miles per hour (mph) relative to a speed of 10 mph. MicroFacPM can also be applied to examine the contribution of emission rates per vehicle class, model year, and sources of PM. The model evaluation is presented for the Tuscarora Mountain Tunnel, Pennsylvania Turnpike, PA, and some limited evaluations at two locations: Sepulveda Tunnel, Los Angeles, CA, and Van Nuys Tunnel, Van Nuys, CA. In general, the performance of MicroFacPM has shown very encouraging results.     

Codependencies of reactive air toxic and criteria pollutants on emission reductions

It is important to understand the effects of emission controls on concentrations of ozone, fine particulate matter (PM2.5), and hazardous air pollutants (HAPs) simultaneously, to evaluate the full range of health, ecosystem, and economic effects. Until recently, the capability to simultaneously evaluate interrelated atmospheric pollutants ("one atmosphere" analysis) was unavailable to air quality managers. In this work, we use an air quality model to examine the potential effect of three emission reductions on concentrations of ozone, PM2.5, and four important HAPs (formaldehyde, acetaldehyde, acrolein, and benzene) over a domain centered on Philadelphia for 12-day episodes in July and January 2001. Although NO(x) controls are predicted to benefit PM2.5 concentrations and sometimes benefit ozone, they have only a small effect on formaldehyde, slightly increase acetaldehyde and acrolein, and have no effect on benzene in the July episode. Concentrations of all pollutants except benzene increase slightly with NO(x) controls in the January simulation. Volatile organic compound controls alone are found to have a small effect on ozone and PM2.5, a less than linear effect on decreasing aldehydes, and an approximately linear effect on acrolein and benzene in summer, but a slightly larger than linear effect on aldehydes and acrolein in winter. These simulations indicate the difficulty in assessing how toxic air pollutants might respond to emission reductions aimed at decreasing criteria pollutants such as ozone and PM2.5.     

Hydrogeochemical comparison and effects of overlapping redox zones on groundwater arsenic near the Western (Bhagirathi sub-basin, India) and Eastern (Meghna sub-basin, Bangladesh) margins of the Bengal Basin

Although arsenic (As) contamination of groundwater in the Bengal Basin has received wide attention over the past decade, comparative studies of hydrogeochemistry in geologically different sub-basins within the basin have been lacking. Groundwater samples were collected from sub-basins in the western margin (River Bhagirathi sub-basin, Nadia, India; 90 samples) and eastern margin (River Meghna sub-basin; Brahmanbaria, Bangladesh; 35 samples) of the Bengal Basin. Groundwater in the western site (Nadia) has mostly Ca-HCO(3) water while that in the eastern site (Brahmanbaria) is much more variable consisting of at least six different facies. The two sites show differences in major and minor solute trends indicating varying pathways of hydrogeochemical evolution However, both sites have similar reducing, postoxic environments (p(e): +5 to -2) with high concentrations of dissolved organic carbon, indicating dominantly metal-reducing processes and similarity in As mobilization mechanism. The trends of various redox-sensitive solutes (e.g. As, CH(4), Fe, Mn, NO(3)(-), NH(4)(+), SO(4)(2-)) indicate overlapping redox zones, leading to partial redox equilibrium conditions where As, once liberated from source minerals, would tend to remain in solution because of the complex interplay among the electron acceptors.     

Temporal trends (1990-2000) in the concentration of cadmium, lead and mercury in mosses across Europe

The European heavy metals in mosses survey provides data on the concentration of 10 heavy metals in naturally growing mosses. The survey has been repeated at five-yearly intervals and in this paper we report on the temporal trends in the concentration of cadmium, lead and mercury between 1990 and 2000. Metal- and country-specific temporal trends were observed. In general, the concentration of lead and cadmium in mosses decreased between 1990 and 2000; the decline was higher for lead than cadmium. For mercury not enough data were available to establish temporal trends between 1990 and 1995, but between 1995 and 2000 the mercury concentration in mosses did not change across Europe. The observed temporal trends for the concentrations in mosses were similar to the trends reported for the modelled total deposition of cadmium, lead and mercury in Europe.     

Motor Vehicle Contributions to Ambient PM10 and PM2.5 at Selected Urban Areas in the USA

A source apportionment study was carried out to estimate the contribution of motor vehicles to ambient particulate matter (PM) in selected urban areas in the USA. Measurements were performed at seven locations during the period September 7, 2000 through March 9, 2001. Measurements included integrated PM_2.5 and PM₁₀ concentrations and polycyclic aromatic hydrocarbons (PAHs). Ambient PM_2.5 and PM₁₀ were apportioned to their local sources using the chemical mass balance (CMB) receptor model and compared with results obtained using scanning electron microscopy (SEM). Results indicate that PM_2.5 components were mainly from combustion sources, including motor vehicles, and secondary species (nitrates and sulfates). PM₁₀ consisted mainly of geological material, in addition to emissions from combustion sources. The fractional contributions of motor vehicles to ambient PM were estimated to be in the range from 20 to 76% and from 35 to 92% for PM_2.5 and PM₁₀, respectively.     

Induction of host specificity in larvae of Manduca sexta: chemical dependence controlling host recognition and developmental rate

Summary. The tobacco hornworm, Manduca sexta L. (Lepidoptera: Sphingidae) is a specialist on Solanaceae. This host specificity is induced as the larva feeds on solanaceous foliage, so that solanaceous-reared larvae will refuse to feed on other plants. Experiments were designed to determine the role of dietary constituents on the induction of host specificity and the effects of these on development of M. sexta. Choice assays using leaf discs of cowpea, Vigna sinensis (Fabaceae), were used to monitor the isolation of relevant chemical cues from foliage of potato. An aqueous extract of potato foliage strongly stimulated feeding. This extract was partitioned with n-butanol under alkaline conditions to obtain a highly active butanol extract. Reversed phase flash chromatography with a water-methanol gradient gave an active fraction that was used as a supplement for wheat germ-based artificial diet. Larvae reared on this s-diet became dependent on potato allelochemicals for initiation and continuation of feeding activity. These larvae also developed faster than larvae reared on the control p-diet, but no effect on adult mass was detected. Further flash chromatography of the active fraction under alkaline conditions provided a highly active sub-fraction, and semi-preparative HPLC using gradients of water and acetonitrile resulted in the isolation of a single compound. Bioassays indicated that this compound alone can account for host recognition by solanaceous-reared larvae. The results suggest that the mechanism of induced host specificity in M. sexta involves development of dependence on this compound. Received 21 December 1999; accepted 14 March 2000     

Magnesium and the regulation of lead in three populations of the garden snail Cantareus aspersus

Helicid snails appear to regulate Pb more closely than other toxic metals, though it is reported as the least toxic. No regulatory mechanism has been described in animals, and the possible role of Mg in limiting Pb assimilation is examined here for the first time. Three populations of Cantareus aspersus were fed Pb and Ca with three levels of Mg for up to 64 days. Metal assimilation and production efficiency was calculated for each of 108 snails. Populations differed in their pattern of uptake but soft tissue Pb was unaffected by dietary Mg. The proportion of Pb assimilated did not change as soft tissue concentrations increased, indicating no specific regulatory mechanism. The daily addition of Pb to the soft tissues increases with growth rate suggesting uptake is instead some function of growth or cell turnover. Bioconcentration factors varied with time and are unreliable indicators of an evolved regulatory mechanism for Pb.