Ambient aerosol size distributions and number concentrations measured during the Pittsburgh Air Quality Study (PAQS)

Twelve months of aerosol size distributions from 3 to 560nm, measured using scanning mobility particle sizers are presented with an emphasis on average number, surface, and volume distributions, and seasonal and diurnal variation. The measurements were made at the main sampling site of the Pittsburgh Air Quality Study from July 2001 to June 2002. These are supplemented with 5 months of size distribution data from 0.5 to 2.5μm measured with a TSI aerosol particle sizer and 2 months of size distributions measured at an upwind rural sampling site. Measurements at the main site were made continuously under both low and ambient relative humidity. The average Pittsburgh number concentration (3-500nm) is 22,000cm-3 with an average mode size of 40nm. Strong diurnal patterns in number concentrations are evident as a direct effect of the sources of particles (atmospheric nucleation, traffic, and other combustion sources). New particle formation from homogeneous nucleation is significant on 30-50% of study days and over a wide area (at least a hundred kilometers). Rural number concentrations are a factor of 2-3 lower (on average) than the urban values. Average measured distributions are different from model literature urban and rural size distributions. © 2004 Elsevier Ltd. All rights reserved.

Pittsburgh air quality study overview

Ambient sampling for the Pittsburgh Air Quality Study (PAQS) was conducted from July 2001 to September 2002. The study was designed (1) to characterize particulate matter (PM) by examination of size, surface area, and volume distribution, chemical composition as a function of size and on a single particle basis, morphology, and temporal and spatial variability in the Pittsburgh region; (2) to quantify the impact of the various sources (transportation, power plants, biogenic sources, etc.) on the aerosol concentrations in the area; and (3) to develop and evaluate the next generation of atmospheric aerosol monitoring and modeling techniques. The PAQS objectives, study design, site descriptions and routine and intensive measurements are presented. Special study days are highlighted, including those associated with elevated concentrations of daily average PM2.5 mass. Monthly average and diurnal patterns in aerosol number concentration, and aerosol nitrate, sulfate, elemental carbon, and organic carbon concentrations, light scattering as well as gas-phase ozone, nitrogen oxides, and carbon monoxide are discussed with emphasis on the processes affecting them. Preliminary findings reveal day-to-day variability in aerosol mass and composition, but consistencies in seasonal average diurnal profiles and concentrations. For example, the seasonal average variations in the diurnal PM2.5 mass were predominately driven by the sulfate component. © 2004 Elsevier Ltd. All rights reserved.

Variability of particulate matter concentrations along roads and motorways determined by a moving measurement unit

The spatial variability of aerosol number and mass along roads was determined in different regions (urban, rural and coastal-marine) of the Netherlands. A condensation particle counter (CPC) and an optical aerosol spectrometer (LAS-X) were installed in a van along with a global positioning system (GPS). Concentrations were measured with high-time resolutions while driving allowing investigations not possible with stationary equipment. In particular, this approach proves to be useful to identify those locations where numbers and mass attain high levels ('hot spots'). In general, concentrations of number and mass of particulate matter increase along with the degree of urbanisation, with number concentration being the more sensitive indicator. The lowest particle numbers and PM1-concentrations are encountered in a coastal and rural area: <5000cm-3 and 6μgm-3, respectively. The presence of sea-salt material along the North-Sea coast enhances PM>1-concentrations compared to inland levels. High-particle numbers are encountered on motorways correlating with traffic intensity; the largest average number concentration is measured on the ring motorway around Amsterdam: about 160000cm-3 (traffic intensity 100000vehday-1). Peak values occur in tunnels where numbers exceed 106cm-3. Enhanced PM1 levels (i.e. larger than 9μgm-3) exist on motorways, major traffic roads and in tunnels. The concentrations of PM>1 appear rather uniformly distributed (below 6μgm-3 for most observations). On the urban scale, (large) spatial variations in concentration can be explained by varying intensities of traffic and driving patterns. The highest particle numbers are measured while being in traffic congestions or when behind a heavy diesel-driven vehicle (up to 600×103cm-3). Relatively high numbers are observed during the passages of crossings and, at a decreasing rate, on main roads with much traffic, quiet streets and residential areas with limited traffic. The number concentration exhibits a larger variability than mass: the mass concentration on city roads with much traffic is 12% higher than in a residential area at the edge of the same city while the number of particles changes by a factor of two (due to the presence of the ultrafine particles (aerodynamic diameter <100nm). It is further indicated that people residing at some 100m downwind a major traffic source are exposed to (still) 40% more particles than those living in the urban background areas. © 2004 Elsevier Ltd. All rights reserved.

Impacts of Mountaintop Removal Coal Mining on the Mud River, West Virginia: Selenium Accumulation, Trophic Transfer, and Toxicity in Fish

Selenium (Se) is a micronutrient necessary for the function of a variety of important enzymes; Se also exhibits a narrow range in concentrations between essentiality and toxicity. Oviparous vertebrates such as birds and fish are especially sensitive to Se toxicity, which causes reproductive impairment and defects in embryo development. Selenium occurs naturally in the Earth's crust, but it can be mobilized by a variety of anthropogenic activities, including agricultural practices, coal burning, and mining.

Mountaintop removal/valley fill (MTR/VF) coal mining is a form of surface mining found throughout central Appalachia in the United States that involves blasting off the tops of mountains to access underlying coal seams. Spoil rock from the mountain is placed into adjacent valleys, forming valley fills, which bury stream headwaters and negatively impact surface water quality. This research focused on the biological impacts of Se leached from MTR/VF coal mining operations located around the Mud River, West Virginia.

In order to assess the status of Se in a lotic (flowing) system such as the Mud River, surface water, insects, and fish samples including creek chub (Semotilus atromaculatus) and green sunfish (Lepomis cyanellus) were collected from a mining impacted site as well as from a reference site not impacted by mining. Analysis of samples from the mined site showed increased conductivity and Se in the surface waters compared to the reference site in addition to increased concentrations of Se in insects and fish. Histological analysis of mined site fish gills showed a lack of normal parasites, suggesting parasite populations may be disrupted due to poor water quality. X-ray absorption near edge spectroscopy techniques were used to determine the speciation of Se in insect and creek chub samples. Insects contained approximately 40-50% inorganic Se (selenate and selenite) and 50-60% organic Se (Se-methionine and Se-cystine) while fish tissues contained lower proportions of inorganic Se than insects, instead having higher proportions of organic Se in the forms of methyl-Se-cysteine, Se-cystine, and Se-methionine.

Otoliths, calcified inner ear structures, were also collected from Mud River creek chubs and green sunfish and analyzed for Se content using laser ablation inductively couple mass spectrometry (LA-ICP-MS). Significant differences were found between the two species of fish, based on the concentrations of otolith Se. Green sunfish otoliths from all sites contained background or low concentrations of otolith Se (< 1 µg/g) that were not significantly different between mined and unmined sites. In contrast creek chub otoliths from the historically mined site contained much higher (≥ 5 µg/g, up to approximately 68 µg/g) concentrations of Se than for the same species in the unmined site or for the green sunfish. Otolith Se concentrations were related to muscle Se concentrations for creek chubs (R2 = 0.54, p = 0.0002 for the last 20% of the otolith Se versus muscle Se) while no relationship was observed for green sunfish.

Additional experiments using biofilms grown in the Mud River showed increased Se in mined site biofilms compared to the reference site. When we fed fathead minnows (Pimephales promelas) on these biofilms in the laboratory they accumulated higher concentrations of Se in liver and ovary tissues compared to fathead minnows fed on reference site biofilms. No differences in Se accumulation were found in muscle from either treatment group. Biofilms were also centrifuged and separated into filamentous green algae and the remaining diatom fraction. The majority of Se was found in the diatom fraction with only about 1/3rd of total biofilm Se concentration present in the filamentous green algae fraction

Finally, zebrafish (Danio rerio) embryos were exposed to aqueous Se in the form of selenate, selenite, and L-selenomethionine in an attempt to determine if oxidative stress plays a role in selenium embryo toxicity. Selenate and selenite exposure did not induce embryo deformities (lordosis and craniofacial malformation). L-selenomethionine, however, induced significantly higher deformity rates at 100 µg/L compared to controls. Antioxidant rescue of L-selenomethionime induced deformities was attempted in embryos using N-acetylcysteine (NAC). Pretreatment with NAC significantly reduced deformities in the zebrafish embryos secondarily treated with L-selenomethionine, suggesting that oxidative stress may play a role in Se toxicity. Selenite exposure also induced a 6.6-fold increase in glutathione-S-transferase pi class 2 gene expression, which is involved in xenobiotic transformation. No changes in gene expression were observed for selenate or L-selenomethionine-exposed embryos.

The findings in this dissertation contribute to the understanding of how Se bioaccumulates in a lotic system and is transferred through a simulated foodweb in addition to further exploring oxidative stress as a potential mechanism for Se-induced embryo toxicity. Future studies should continue to pursue the role of oxidative stress and other mechanisms in Se toxicity and the biotransformation of Se in aquatic ecosystems.