Towards a better understanding of tetrachloroethene entry pressure in the matrix of Permo-Triassic sandstones

The pressure required for a chlorinated solvent to enter a geological medium can be calculated given knowledge of the characteristic pore size of the medium and the interfacial tension (IFT) and contact angle of the solvent-water-rock system. Using a centrifuge-based method, capillary pressure-saturation curves have been determined for 30 water-saturated samples of Permo-Triassic sandstones for the solvent tetrachloroethene (PCE). These curves have been successfully fitted using the van Genuchten function to determine PCE entry pressure for each of the sandstone samples. A plot of PCE entry pressures against average pore diameter shows a linear relationship in log-log space; however, observed values for PCE entry pressure are significantly lower than would be expected theoretically for a sandstone-PCE-water system. This may be explained either by a decrease in the IFT or an increase in the contact angle. The IFT may decrease during contact with sandstones due to hysteresis effects during imbibition and drainage of fluids, but this is unlikely to be sufficient to account for the low entry pressures observed. Therefore, it is inferred that the low observed PCE entry pressures are due to higher than expected PCE contact angles, and that the average pore-throat surface of the sandstones is more solvent wetting than would be expected. A weak acid extraction indicates the presence of calcite and dolomite in the sandstone cores, and a correlation is observed between carbonate content per unit porosity and a reduction in PCE entry pressure. It is suggested that these mineral phases are responsible for observed wettability changes and a conceptual model is proposed. One consequence of the lower observed entry pressures is that solvents are likely to penetrate deeper into the matrix of water-saturated sandstones than previously expected.     

Real-world vehicle emissions: a summary of the Eleventh Coordinating Research Council On-Road Vehicle Emissions Workshop

The Coordinating Research Council (CRC) held its eleventh workshop in March 2001, focusing on results from the most recent real-world vehicle emissions research. We summarize the presentations from researchers engaged in improving our understanding of the contribution of mobile sources to ambient air quality and emission inventories. Participants in the workshop discussed efforts to improve mobile source emission models and emission inventories, the role of on-board diagnostic (OBD) systems in inspection and maintenance (I/M) programs, particulate matter (PM) emissions, contributions of diesel vehicles to the emission inventory, on-road emissions measurements, fuel effects, unregulated emissions, and microscale and modal emission models, as well as topics for future research.     

Determination of acute exposure guideline levels in a dispersion model

The U.S. Environmental Protection Agency (EPA) is in the process of establishing acute exposure guideline levels (AEGLs) for a number of toxic chemicals. These guidelines represent predictable human consequences from measured exposures of selected toxic chemicals over time. They are intended for emergency planning and regulatory purposes. This paper presents a method that can be used by atmospheric dispersion models to compute AEGL values and graphically display the regions exposed to each guideline level on area maps. EPA currently defines three levels of AEGLs corresponding to increasingly severe symptoms, ranging from notable discomfort (AEGL-1) to serious adverse health effects (AEGL-2) to life-threatening effects or death (AEGL-3). For each chemical's three AEGL levels, guideline concentrations are defined for five exposure durations: 10 min, 30 min, 1 hr, 4 hr, and 8 hr. Dispersion models can compute a chemical dosage (time-integrated concentration) and a peak concentration throughout the area exposed to the plume. The AEGL then can be computed by finding the effective duration of the plume at each location, computing the AEGL-equivalent dosages for these durations, and comparing the dosage at each point with the AEGL-equivalent dosages. AEGL contours then can be plotted and readily interpreted in terms of expected toxicity levels for each level of health impact.     

Case study II: application of the divalent cation bridging theory to improve biofloc properties and industrial activated sludge system performance-using alternatives to sodium-based chemicals.

The objective of this study was to investigate the application of the divalent cation bridging theory (DCBT) as a tool in the chemical selection process at an activated sludge plant to improve settling, dewatering, and effluent quality. According to the DCBT, to achieve improvements, the goal of chemical selection should be to reduce the ratio of monovalent-to-divalent (M/D) cations. A study was conducted to determine the effect of using magnesium hydroxide [Mg(OH)2] as an alternative to sodium hydroxide (NaOH) at a full-scale industrial wastewater treatment plant. Floc properties and treatment plant performance were measured for approximately one year during two periods of NaOH addition and Mg(OH)2 addition. A cost analysis of plant operation during NaOH and Mg(OH)2 use was also performed. During NaOH addition, the M/D ratio was 48, while, during Mg(OH)2 addition, this ratio was reduced to an average of approximately 0.1. During the Mg(OH)2 addition period, the sludge volume index, effluent total suspended solids, and effluent chemical oxygen demand were reduced by approximately 63, 31, and 50%, respectively, compared to the NaOH addition period. The alum and polymer dose used for clarification was reduced by approximately 50 and 60%, respectively, during Mg(OH)2 addition. The dewatering properties of the activated sludge improved dewatering as measured by decreased capillary suction time and specific resistance to filtration (SRF), along with an increase in cake solids from the SRF test. This corresponded to a reduction in the volume of solids thickened by centrifuges at the treatment plant, which reduced the disposal costs of solids. Considering the costs for chemicals and solids disposal, the annual cost of using Mg(OH)2 was approximately 30,000 dollars to 115,000 dollars less than using NaOH, depending on the pricing of NaOH. The results of this study confirm that the DCBT is a useful tool for assessing chemical-addition strategies and their potential effect on activated sludge performance.     

Isotopic evidence for niche partitioning and the influence of anthropogenic disturbance on endemic and introduced rodents in central Madagascar

We applied a multi-isotope approach to examine aspects of niche partitioning, competition, and mobility for rodents in the Central Highlands of Madagascar. Specifically, we used carbon (δ¹³C), nitrogen (δ¹⁵N), and strontium (⁸⁷Sr/⁸⁶Sr) isotope ratios in bone to investigate diet and mobility for endemic tufted tail rats (Eliurus spp.), and introduced black rats (Rattus rattus) and house mice (Mus musculus) within and outside a fragment of montane humid forest in the Ambohitantely Special Reserve. There was a clear spatial segregation in trapping success for different species: Eliurus was only in the forest interior and edge, Mus only outside of the fragment in a marsh and park housing complex, and Rattus in all habitats except the housing complex. We find only moderate support for mobility of rodents among habitats. Mus may routinely move between the marsh and housing complex. However, regular movement between the forest edge and interior, or between the forest fragment and surrounding grassland is not supported. Taxa appear to target different foods: Rattus tends to feed at a higher trophic level than Eliurus, and Mus consumes some C₄ resources. To date, strontium isotopes have been underutilized in ecological research. Here, we show that they are highly complementary to carbon and nitrogen isotope data. Even in localities with relatively uniform underlying geology, it may be possible to distinguish individuals that regularly forage in different habitats.     

Organochlorine contamination in shorebirds from Washington state and the significance for their falcon predators

Arctic-breeding shorebirds collected in western Washington state during winter and spring, and a comparative sample collected in coastal California during the winter were analyzed for organochlorine contaminants to determine the potential impact of these residues on populations of peregrine falcons (Falco peregrinus) and merlins (F. columbarius) which prey upon shorebirds in western Washington. Dunlins (Calidris alpina), an important winter prey for falcons in western Washington, were collected between 1975 and 1981. During winter 1980–81, dunlins carried low organochlorine residues; DDE levels ranged from 0.01 to 1.2 ppm, and PCB levels ranged from 0.02 to 0.82 ppm (wet weight). Levels of other organochlorine contaminants (HCB, Chlordane compounds, Dieldrin, and Heptachlor Epoxide), analyzed in a subsample of dunlins, were consistently lower than DDE and PCB levels, and ranged from 0.001 to 0.22 ppm (wet weight). Dunlins in western Washington did not significantly increase their DDE or PCB burdens over the 1980–81 winter. A decline in DDE residues between 1978 and 1981 was noted, and declines in PCB residues from both 1975 and 1978 to 1980–81 were noted. Residues in other wintering shorebirds from western Washington were similar. Wintering sanderlings (Calidris alba) from California, revealed much higher DDE contamination than in Washington (up to 32 ppm, wet weight). Spring migrant shorebirds in western Washington contained both low and very high DDE residues (up to 417 ppm, wet weight). There is evidence suggesting these high DDE concentrations are accumulated along the Pacific coast of North America.     

Pollution and Genetic Structure of North American Populations of the Common Dandelion (Taraxacum Officinale)

Assessing the genetic structure of natural populations differentially impacted by anthropogenic contaminants can be a useful tool for evaluating the population genetic consequences of exposure to pollution. In this study, measures of genetic diversity at variable-number-tandem-repeat loci in six dandelion populations (3 urban and 3 rural) showed patterns that may have been influenced by exposure to environmental contaminants. Mean genetic similarity among individuals within a population was significantly and positively correlated with increasing levels of airborne particulate matter ( 10 m, PM₁₀) and soil concentrations of four metals (Cd, Fe, Ni and Pb). In addition, mean genetic similarity was always significantly higher at the urban sites compared to rural sites. There was a significant negative correlation between the number of genotypes at a site and increasing amounts of PM₁₀, concentrations of five soil metals (Cd, Cu, Fe, Ni and Pb), leaf tissue levels of Fe and a significant positive correlation between the extent of clonality at a site and levels of PM₁₀ and soil concentrations of five metals (Cd, Cu, Fe, Ni and Pb). Although, this study does not directly establish a causal link between the specific contaminants detected at the study sites and differences in genetic diversity, our data are consistent with the hypothesis that pollution-induced selection has contributed in some fashion to the lower genetic diversity found at the urban sites.     

Occurrence and persistence of perfluorooctanesulfonate and other perfluorinated surfactants in groundwater at a fire-training area at Wurtsmith Air Force Base,Michigan, USA

Various formulations of fire-extinguishing materials, including aqueous film-forming foams (AFFFs), were used as part of fire-training exercises conducted at Wurtsmith Air Force Base (WAFB) in northeastern Michigan from the 1950s until the base was decommissioned in 1993. As a result of past fire-training exercises, AFFF-laden wastewater containing fuels, solvents, and other materials directly entered groundwater without prior treatment. Perfluorinated surfactants are key components in some AFFF formulations. In this study, groundwater was analyzed for perfluoroalkanesulfonates and perfluorocarboxylates. Perfluoroalkanesulfonates were directly detected using negative-ion electrospray ionization mass spectrometry. Derivatized perfluorocarboxylates were detected using electron impact gas chromatography-mass spectrometry. Groundwater from wells around fire-training area FTA-02 at WAFB contained four perfluorinated surfactants ranging in concentration from 3 to 120 microg L(-1): perfluorooctanesulfonate (PFOS); perfluorohexanesulfonate; perfluorooctanoate; and perfluorohexanoate. This is the first report demonstrating that PFOS, recently shown to be toxic to organisms ranging from zooplankton to primates, is still present in groundwater in measurable quantities five or more years after its last known use.     

Monitoring dissolved copper concentrations in Chesapeake Bay,U.S.A.

Dissolved copper and selected water chemistry parameters were monitored for 11 months in Chesapeake Bay, U.S.A. Dissolved copper concentrations in four recreational marinas, a large harbor, two major river systems, and a heavily used shipping canal ranged from below detectable levels to 80 g L^-1 (\-X=11.7 g L^-1). Dissolved copper was detected >91% of the time at five locations. Lowest copper concentrations were found in Potomac River, Baltimore Harbor, Pier One Marina, and C & D Canal (\-X=6–10 g L^-1; slightly higher levels of dissolved copper were found in Choptank River (\-X=12 g L^-1). Highest levels of copper were detected in Port Annapolis, Hartge, and Piney Narrows Marinas (\-X=13–18 g L^-1), with the highest values observed in the study (70 and 80 g L^-1) found in two of these marinas. Copper in the three marinas with highest dissolved copper levels could have been toxic to some of the more sensitive aquatic species. Intensive study of one marina indicated that a likely source of dissolved copper was the recreational boats housed in the marina.