Spatial distribution of polybrominated diphenyl ethers and polybrominated biphenyls in lake trout from the Laurentian Great Lakes

Concentrations of two types of brominated flame-retardants (BFRs); polybrominated diphenyl ethers (PBDEs) and polybrominated biphenyls (PBBs) were determined in a single age class of lake trout (Salvelinus namaycush) collected from the Laurentian Great Lakes in 1997. Mean concentrations of total PBDE were highest in samples from Lake Ontario at 95+/-22 ng/g wet weight (ww) or 434+/-100 ng/g lipid weight (lw) while the lowest concentrations were observed in Lake Erie lake trout (27+/-8.6 ng/g ww, 117+/-37 ng/g lw). In all samples, the predominant PBDE congeners were 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), and 2,2',4,4', 6-pentabromodiphenyl ether (BDE-100), which are the primary components of the commonly used penta-BDE formulation flame retardant. Lake trout collected from Lake Huron had the highest concentrations of PBBs (3.1+/-1.7 ng/g ww, 15+/-8.5 ng/g lw), while the lowest levels were detected in fish from Lake Superior (0.25+/-0.13 ng/g ww, 1.7+/-0.89 ng/g lw). In all lake trout samples, 2,2',4,4',5,5'-hexabromobiphenyl (BB-153), a major constituent of the flame-retardant FireMaster BP-6, was the predominant PBB congener.     

Heterogeneity of chlorinated hydrocarbon sorption properties in a sandy aquifer

Hydraulic conductivity and sorption coefficients for chlorinated hydrocarbons (chloroform, carbon tetrachloride and tetrachloroethylene) were evaluated for 216 sediment samples collected across a 15 m transect and a 21 m depth interval in a contaminated aquifer near Schoolcraft, Michigan. Relationships between hydraulic conductivity, linear sorption partition coefficients, grain size classes, and spatial location were investigated using linear regression analysis and geostatistical techniques. Clear evidence of layering was found in sorption properties, hydraulic conductivity and grain sizes. Conductivity correlated well with grain size, as expected, but sorption varied inversely with grain size, contrary to some previous reports. No significant correlation was found between sorption properties and hydraulic conductivity. This is likely due to the unexpected presence of small amounts of highly sorptive coal-like solids, which dominate the sorption behavior but have little effect on conductivity. The results demonstrate that recent findings regarding the high sorption capacity of coal materials found in soils can exert a controlling influence on contaminant transport. Designers of in situ remediation systems should be cautioned that 1) it is not reasonable to assume that sorption capacity and hydraulic conductivity are related, 2) sorption capacity and hydraulic conductivity are critical measurements for contaminant site characterization and subsequent transport modeling, 3) estimating sorption capacity from organic carbon measurement may lead to greater errors than performing sorption isotherms, and 4) it is more important to characterize vertical heterogeneity rather than horizontal heterogeneity because both sorption and hydraulic conductivity are correlated across longer distances in the horizontal plane.     

Persistence of carbofuran in marine sand and water

Marine sand and seawater samples were collected in March 2002 from Laysan Island in the Hawaiian Islands National Wildlife Refuge, where a small area was contaminated by the carbamate insecticide carbofuran. Carbofuran was still detected at microg g(-1) levels in the Laysan sand after its identification in 1998 and initial observation of the toxicity in 1988. The persistence of carbofuran in the marine sand was investigated in the dark in a 30 degrees C oven, and in distilled deionized water and seawater samples exposed to artificial 300 nm light and to direct sunlight. The laboratory study showed a half-life (t1/2) of approximately 40 days for carbofuran in the native sand and in Ottawa sand. The photolysis of carbofuran was faster in seawater than in distilled deionized water when it was exposed to 300 nm light (t1/2, 0.1 vs. 3.1 h) and to direct sunlight (t1/2, 7.5 vs. 41.6 h). The large difference between the laboratory results and the field observation of carbofuran dissipation suggests that carbofuran degradation at the remote, undisturbed marine site may be governed by its unique environmental factors.     

Development of the IM147: an alternative inspection/maintenance mass-emission transient test to address vehicle preconditioning concerns

A series of studies was performed to develop an alternative to the U.S. Environmental Protection Agency's gold standard IM240 mass-based emission test. The new IM147 test was based on the second phase of the IM240 that consists of 147 sec of transient vehicle operation. Paired IM240/IM147 tests were conducted on vehicles ranging from 1981 to 1996 to determine IM147 cutpoints and excess emissions were identified. Additionally, an optimized test procedure was developed that combined possible triplicate IM147s with improved drive trace quality control, fast-pass, and retest methods. The optimized procedure was found to provide improved vehicle preconditioning with a relatively minor decrease in excess emissions identification. Resulting identification rates ranged from 96 to 100% for hydrocarbons (HC), 93-100% for CO, and 93-100% for NOx, depending on cutpoint selection, while false failures caused by lack of vehicle preconditioning were reduced to essentially zero. Significant vehicle throughput improvements were achieved through the development of software algorithms involving modal fast-pass and retest procedures. Modal drive trace variation limits also were developed to improve test accuracy. The combination of the algorithms reduced average IM147 test times by nearly 60%.     

Ah receptor for 2,3,7,8-tetrachlorodibenzo-p-dioxin: Comparative studies in mammalian and nonmammalian species

The Ah receptor was identified and characterized in cytosol from a large number of diverse animal species. Molecular properties of the Ah receptor were similar in all species which had detectable receptor. However, subtle differences in receptor properties exist among animal species and these differences indicate that the Ah receptor protein is not identical in all species. It is not yet known whether differences in receptor properties among animal species play a significant role in determining differential susceptibility of the species to toxicity from halogenated aromatic compounds.     

Analysis of Ah receptor pathway activation by brominated flame retardants

Brominated flame-retardants (BFRs) are used as additives in plastics to decrease the rate of combustion of these materials, leading to greater consumer safety. As the use of plastics has increased, the production and use of flame-retardants has also grown. Many BFRs are persistent and have been detected in environmental samples, raising concerns about the biological/toxicological risk associated with their use. Most BFRs appear to be non-toxic, however there is still some concern that these compounds, or possible contaminants in BFRs mixtures could interact with cellular receptors. In this study we have examined the interaction of decabromodiphenyl ether, Firemaster BP4A (tetrabromobisphenol A), Firemaster PHT4 (tetrabromophthalic anhydride), hexabromobenzene, pentabromotoluene, decabromobiphenyl, Firemaster BP-6 (2,2^′,4,4^′,5,5^′-hexabromobiphenyl) and possible contaminants of BFR mixtures with the Ah receptor. Receptor binding and activation was examined using the Gel Retardation Assay and increased expression of dioxin responsive genes was detected using the reporter gene based CALUX assay. The results demonstrate the ability of BFRs to activate the AhR signal transduction pathway at moderate to high concentrations as assessed using both assays. AhR-dependent activation by BFRs may be due in part to contaminants present in commercial/technical mixtures. This was suggested by our comparative analysis of Firemaster BP-6 versus its primary component 2,2^′,4,4^′,5,5^′-hexabromobiphenyl. Some technical mixtures of brominated flame-retardants contain brominated biphenyls, dioxins or dibenzofurans as contaminants. When tested in the CALUX assay these compounds were found to be equivalent to, or more active than their chlorinated analogues. Relative effective potency values were determined from dose response curves for these brominated HAHs.     

A new method for the rapid determination of volatile organic compound breakthrough times for a sorbent at concentrations relevant to indoor air quality

The use of sorbents has been proposed to remove volatile organic compounds (VOCs) present in ambient air at concentrations in the parts-per-billion (ppb) range, which is typical of indoor air quality applications. Sorbent materials, such as granular activated carbon and molecular sieves, are used to remove VOCs from gas streams in industrial applications, where VOC concentrations are typically in the parts-per-million range. A method for evaluating the VOC removal performance of sorbent materials using toluene concentrations in the ppb range is described. Breakthrough times for toluene at concentrations from 2 to 7500 ppb are presented for a hydrophobic molecular sieve at 25%) relative humidity. By increasing the ratio of challenge gas flow rate to the mass of the sorbent bed and decreasing both the mass of sorbent in the bed and the sorbent particle size, this method reduces the required experimental times by a factor of up to several hundred compared with the proposed American Society of Heating, Refrigerating, and Air-Conditioning Engineers method, ASHRAE 145P, making sorbent performance evaluation for ppb-range VOC removal more convenient. The method can be applied to screen sorbent materials for application in the removal of VOCs from indoor air.     

Impact of engine lubricant properties on regulated gaseous emissions of 2000-2001 model-year gasoline vehicles

The impact of the sulfur (S) content in lubricating oil was evaluated for four ultra-low-emission vehicles and two super-ultra-low-emission vehicles, all with low mileage. The S content in the lube oils ranged from 0.01 to 0.76%, while the S content of the gasoline was fixed at 0.2 ppmw. Vehicles were configured with aged catalysts and tested over the Federal Test Procedure, at idle and at 50-mph cruise conditions. In all testing modes, variations in the S level of the lubricant did not significantly affect the regulated gas-phase tailpipe emissions. In addition to the regulated gas-phase emissions, a key element of the research was measuring the engine-out sulfur dioxide (SO2) in near-real-time. This research used a new methodology based on a differential optical absorption spectrometer (DOAS) to measure SO2 from the lubricants used in this study. With the DOAS, the contribution of SO2 emissions for the highest-S lubricant was found to range from less than 1 to 6 ppm on a gasoline S equivalent basis over the range of vehicles and test cycles used. The development and operation of the DOAS is discussed in this paper.