Distribution and transport of coal tar-derived PAHs in fine-grained residuum

We investigated the distribution and transport of coal tar-derived polycyclic aromatic hydrocarbons (PAHs) in fine-grained residuum and alluvial floodplain deposits that underlie a former manufactured gas plant. All 16 USEPA priority pollutant PAHs are present at this site and have penetrated the entire 4-5m thickness of clayey sediments, which unconformably overly limestone bedrock. Concentrations of less hydrophobic PAHs (e.g., naphthalene, 0.011-384mg kg(-1)) were about 10 times higher than those of highly hydrophobic PAHs (e.g., benzo[g,h,i]perylene -0.002 to 56.03mgkg(-1)). Microscopic examination of thin-sections of the clay-rich sediments showed that fractures and rootholes, which can act as pathways for flow, occur throughout the profiles. Tarry residue was found coating some fractures and rootholes, indicating that coal tar was, in some cases, able to penetrate as an immiscible phase. However, in the vast majority of samples in which PAHs were detected, there was no detectable tar residue, suggesting that much of the transport occurred in the dissolved phase. Examination of thin-sections with an epifluorescent microscope indicated that PAHs, which fluoresce brightly when exposed to UV light, are distributed throughout the soil matrix, rather than being confined to fractures and rootholes. The widespread distribution of PAHs is most likely due to diffusion-controlled exchange between the fast-flow pathways in the fractures and rootholes and the relatively immobile water in the fine-grained matrix. This implies that fractures and rootholes can play a major role in controlling transport of highly hydrophobic compounds in fine-grained sediments, which would otherwise act as barriers to contaminant migration.     

Linking ground-water age and chemistry data along flow paths: implications for trends and transformations of nitrate and pesticides

Tracer-based ground-water ages, along with the concentrations of pesticides, nitrogen species, and other redox-active constituents, were used to evaluate the trends and transformations of agricultural chemicals along flow paths in diverse hydrogeologic settings. A range of conditions affecting the transformation of nitrate and pesticides (e.g., thickness of unsaturated zone, redox conditions) was examined at study sites in Georgia, North Carolina, Wisconsin, and California. Deethylatrazine (DEA), a transformation product of atrazine, was typically present at concentrations higher than those of atrazine at study sites with thick unsaturated zones but not at sites with thin unsaturated zones. Furthermore, the fraction of atrazine plus DEA that was present as DEA did not increase as a function of ground-water age. These findings suggest that atrazine degradation occurs primarily in the unsaturated zone with little or no degradation in the saturated zone. Similar observations were also made for metolachlor and alachlor. The fraction of the initial nitrate concentration found as excess N2 (N2 derived from denitrification) increased with ground-water age only at the North Carolina site, where oxic conditions were generally limited to the top 5 m of saturated thickness. Historical trends in fluxes to ground water were evaluated by relating the times of recharge of ground-water samples, estimated using chlorofluorocarbon concentrations, with concentrations of the parent compound at the time of recharge, estimated by summing the molar concentrations of the parent compound and its transformation products in the age-dated sample. Using this approach, nitrate concentrations were estimated to have increased markedly from 1960 to the present at all study sites. Trends in concentrations of atrazine, metolachlor, alachlor, and their degradates were related to the timing of introduction and use of these compounds. Degradates, and to a lesser extent parent compounds, were detected in ground water dating back to the time these compounds were introduced.     

Regulatory effects of dioxin-like and non-dioxin-like PCBs and other AhR ligands on the antioxidant enzymes paraoxonase 1/2/3

Paraoxonase 1 (PON1), an antioxidant enzyme, is believed to play a critical role in many diseases, including cancer. PCBs are widespread environmental contaminants known to induce oxidative stress and cancer and to produce changes in gene expression of various pro-oxidant and antioxidant enzymes. Thus, it appeared of interest to explore whether PCBs may modulate the activity and/or gene expression of PON1 as well. In this study, we compared the effects of dioxin-like and non-dioxin-like PCBs and of various aryl hydrocarbon receptor (AhR) ligands on PON1 regulation and activity in male and female Sprague-Dawley rats. Our results demonstrate that (i) the non-dioxin-like PCB154, PCB155, and PCB184 significantly reduced liver and serum PON1 activities, but only in male rats; (ii) the non-dioxin-like PCB153, the most abundant PCB in many matrices, did not affect PON1 messenger RNA (mRNA) level in the liver but significantly decreased serum PON1 activity in male rats; (iii) PCB126, an AhR ligand and dioxin-like PCB, increased both PON1 activities and gene expression; and (iv) even though three tested AhR ligands induced CYP1A in several tissues to a similar extent, they displayed differential effects on the three PONs and AhR, i.e., PCB126 was an efficacious inducer of PON1, PON2, PON3, and AhR in the liver, while 3-methylcholantrene induced liver AhR and lung PON3, and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), the most potent AhR agonist, increased only PON3 in the lung, at the doses and exposure times used in these studies. These results show that PCBs may have an effect on the antioxidant protection by paraoxonases in exposed populations and that regulation of gene expression through AhR is highly diverse.     

Effect of Common Chemical Treatments on the Process Kinetics and Mechanical Properties of Flax/Epoxy Composites Manufactured by Resin Infusion

Chemical treatments are widely employed to improve the fiber-matrix adhesion in composites based on eco-friendly fibers such as flax. To better understand the influence of these treatments on processing behavior, this study characterized the surface chemistry and morphology of woven flax fabrics treated by acetone, alkaline, silane and diluted epoxy. Flax/epoxy composites were then manufactured by resin infusion and the flow front and preform thickness evolution was monitored. The alkaline treatment was shown to result in a 50 % increase in equivalent permeability due to an increase in porosity which led to a decrease in flexural properties. The processing results were found to be in good agreement with predictions of a 1-dimensional model. This study suggests that infusion times are not considerably affected by the observed changes in surface energy. However, other implications of the treatments such as an increase in fibrillation can alter the infusion times significantly.

     

Spatial distribution of metals within the liver acinus and their perturbation by PCB126

Animal studies show that exposure to the environmental pollutant 3,3′,4,4′,5-pentachlorobiphenyl (PCB126) causes alterations in hepatic metals as measured in acid-digested volume-adjusted tissue. These studies lack the detail of the spatial distribution within the liver. Here we use X-ray fluorescence microscopy (XFM) to assess the spatial distribution of trace elements within liver tissue. Liver samples from male Sprague Dawley rats, treated either with vehicle or PCB126, were formalin fixed and paraffin embedded. Serial sections were prepared for traditional H&E staining or placed on silicon nitride windows for XFM. With XFM, metal gradients between the portal triad and the central vein were seen, especially with copper and iron. These gradients change with exposure to PCB126, even reverse. This is the first report of how micronutrients vary spatially within the liver and how they change in response to toxicant exposure. In addition, high concentrations of zinc clusters were discovered in the extracellular space. PCB126 treatment did not affect their presence, but did alter their elemental makeup suggesting a more general biological function. Further work is needed to properly evaluate the gradients and their alterations as well as classify the zinc clusters to determine their role in liver function and zinc homeostasis.     

Effects of Nighttime Chemistry upon the Transport of Ozone and Ozone Precursors

It has been recognized for several years that ozone in rural areas can exceed the National Ambient Air Quality Standard (NAAQS) for photochemical oxidant whirh was 0.08 ppm for one hour, not to be exceeded more than once per year. During the summer of 1973, the NAAQS was exceeded from 15 to 37% of the time at four rural monitoring sites in Maryland, Pennsylvania, Ohio, and West Virginia.¹ This is a greater violation rate than is found in many urban areas. Dimitriades and Altshuller² have enumerated four possible sources for this rural ozone: (a) transport from urban areas, (b) local photochemical generation from urban ozone precursors, (c) local photochemical generation from precursors of rural origin which may be man-made or natural, and (d) injection of stratospheric ozone into the rural area. This paper considers the chemistry pertinent to the first two of these possible sources of rural ozone, namely the long distance (overnight) transport of ozone and ozone precursors.     

Improving Baghouse Performance at the Monticello Generating Station

At the Monticello station, operated by the Texas Utilities Generating Company, lignite coal obtained locally in Titus and Hopkins Counties fuels each of the three units. Units 1 and 2 are identical 575-MW Combustion Engineering (CE) boilers, each of which discharges its effluent to a 36- compartment shake/deflate cleaned baghouse paralleled with four electrostatic precipitators (ESP). Unit 3 is a larger boiler and is followed by an ESP and a scrubber. The Unit 1 and 2 baghouses were designed to clean 80 percent of the flue gas. Since startup, these baghouses have regularly experienced flange-to-flange pressure drops in excess of 10 in. H₂O, with large opacity spikes caused by ash bleeding through the bags after compartment cleanings. Because of higher-than-expected pressure drop, the baghouses receive only about 45-50 percent of the flue gas. Analysis has shown the Monticello lignite ash significantly differs from most other coal ashes. Testing has shown that the Monticello ash is not filtered effectively by many "standard" bag materials. However, this testing indicates that there are fabrics that show promise of eliminating the ash bleedthrough with little pressure drop penalty. Testing has also shown that injection of low concentrations (10-15 ppm) of ammonia (NH₃) into the flue gas significantly decreases ash bleedthrough, so that with NH₃ injection "standard" bag materials may perform adequately. Currently, fullcompartment testing of four fabrics, with and without NH₃ injection, is under way at the Unit 1 baghouse. The research conducted at the Monticello station is reviewed in this paper and the encouraging results from the full-compartment tests are presented.     

Characterization of PM2.5-bound polycyclic aromatic hydrocarbons in Atlanta—Seasonal variations at urban,suburban, and rural ambient air monitoring sites

Twenty-eight polycyclic aromatic hydrocarbons (PAH) and methylated PAHs (Me-PAH) were measured in daily PM_2.5 samples collected at an urban site, a suburban site, and a rural site in and near Atlanta during 2004 (5 samples/month/site). The suburban site, located near a major highway, had higher PM_2.5-bound PAH concentrations than did the urban site, and the rural site had the lowest PAH levels. Monthly variations are described for concentrations of total PAHs (∑PAHs) and individual PAHs. PAH concentrations were much higher in cold months than in warm months, with average monthly ∑PAH concentrations at the urban and suburban-highway monitoring sites ranging from 2.12 to 6.85 ng m^?3 during January–February and November–December 2004, compared to 0.38–0.98 ng m^?3 during May–September 2004. ∑PAH concentrations were found to be well correlated with PM_2.5 and organic carbon (OC) within seasons, and the fractions of PAHs in PM_2.5 and OC were higher in winter than in summer. Methyl phenanthrenes were present at higher levels than their un-substituted homologue (phenanthrene), suggesting a petrogenic (unburned petroleum products) input. Retene, a proposed tracer for biomass burning, peaked in March, the month with the highest acreage and frequency of prescribed burning and unplanned fires, and in December, during the high residential wood-burning season, indicating that retene might be a good marker for burning of all biomass materials. In contrast, potassium peaked only in December, indicating that it might be a more specific tracer for wood-burning.     

Evaluating inter-continental transport of fine aerosols:(2) Global health impact

In this second of two companion papers, we quantify for the first time the global impact on premature mortality of the inter-continental transport of fine aerosols (including sulfate, black carbon, organic carbon, and mineral dust) using the global modeling results of (Liu et al., 2009). Our objective is to estimate the number of premature mortalities in each of ten selected continental regions resulting from fine aerosols transported from foreign regions in approximately year 2000. Our simulated annual mean population-weighted (P-W) concentrations of total PM2.5 (aerosols with diameter less than 2.5 μm) are highest in East Asia (EA, 30 μg m^?3) and lowest in Australia (3.6 μg m^?3). Dust is the dominant component of PM2.5 transported between continents. We estimate global annual premature mortalities (for adults age 30 and up) due to inter-continental transport of PM2.5 to be nearly 380 thousand (K) in 2000. Approximately half of these deaths occur in the Indian subcontinent (IN), mostly due to aerosols transported from Africa and the Middle East (ME). Approximately 90K deaths globally are associated with exposure to foreign (i.e., originating outside a receptor region) non-dust PM2.5. More than half of the premature mortalities associated with foreign non-dust aerosols are due to aerosols originating from Europe (20K), ME (18K) and EA (15K); and nearly 60% of the 90K deaths occur in EA (21K), IN (19K) and Southeast Asia (16K). The lower and higher bounds of our estimated 95% confidence interval (considering uncertainties from the concentration–response relationship and simulated aerosol concentrations) are 18% and 240% of the estimated deaths, respectively, and could be larger if additional uncertainties were quantified. We find that in 2000 nearly 6.6K premature deaths in North America (NA) were associated with foreign PM2.5 exposure (5.5K from dust PM2.5). NA is least impacted by foreign PM2.5 compared to receptors on the Eurasian continent. However, the number of premature mortalities associated with foreign aerosols in NA (mostly occurring in the U.S.) is comparable to the reduction in premature mortalities expected to result from tightening the U.S. 8-h O₃ standard from 0.08 ppmv to 0.075 ppmv. International efforts to reduce inter-continental transport of fine aerosol pollution would substantially benefit public health on the Eurasian continent and would also benefit public health in the United States.     

Evaluation of a Watershed Model for Estimating Daily Flow Using Limited Flow Measurements1

Abstract: The Soil and Water Assessment Tool (SWAT) model was evaluated for estimation of continuous daily flow based on limited flow measurements in the Upper Oyster Creek (UOC) watershed. SWAT was calibrated against limited measured flow data and then validated. The Nash‐Sutcliffe model Efficiency (NSE) and mean relative error values of daily flow estimations were 0.66 and 15% for calibration, and 0.56 and 4% for validation, respectively. Also, further evaluation of the model’s estimation of flow at multiple locations was conducted with parametric paired t‐test and nonparametric sign test at a 95% confidence level. Among the five main stem stations, four stations were statistically shown to have good agreement between predicted and measured flows. SWAT underestimated the flow of the fifth main stem station possibly because of the existence of complex flood control measures near to the station. SWAT estimated the daily flow at one tributary station well, but with relatively large errors for the other two tributaries. The spatial pattern of predicted flows matched the measured ones well. Overall, it was concluded from the graphical comparisons and statistical analyses of the model results that SWAT was capable of reproducing continuous daily flows based on limited flow data as is the case in the UOC watershed.