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Inside-sediment partitioning of PAH, PCB and organochlorine compounds and inferences on sampling and normalization methods
2011
Opel, Oliver | Palm, Wolf-Ulrich | Steffen, Dieter | Ruck, Wolfgang K.L.
Comparability of sediment analyses for semivolatile organic substances is still low. Neither screening of the sediments nor organic-carbon based normalization is sufficient to obtain comparable results. We are showing the interdependency of grain-size effects with inside-sediment organic-matter distribution for PAH, PCB and organochlorine compounds. Surface sediment samples collected by Van-Veen grab were sieved and analyzed for 16 PAH, 6 PCB and 18 organochlorine pesticides (OCP) as well as organic-matter content. Since bulk concentrations are influenced by grain-size effects themselves, we used a novel normalization method based on the sum of concentrations in the separate grain-size fractions of the sediments. By calculating relative normalized concentrations, it was possible to clearly show underlying mechanisms throughout a heterogeneous set of samples. Furthermore, we were able to show that, for comparability, screening at <125 μm is best suited and can be further improved by additional organic-carbon normalization.
显示更多 [+] 显示较少 [-]The performance of passive flow monitors and phosphate accumulating passive samplers when exposed to pulses in external water flow rate and/or external phosphate concentrations
2011
O’Brien, Dominique | Hawker, Darryl | Shaw, Melanie | Mueller, Jochen F.
Passive samplers are typically calibrated under constant flow and concentration conditions. This study assessed whether concentration and/or flow pulses could be integrated using a phosphate passive sampler (P-sampler). Assessment involved three 21-day experiments featuring a pulse in flow rate, a pulse of filterable reactive phosphate (FRP) concentration and a simultaneous concentration and flow pulse. FRP concentrations were also determined by parallel grab sampling and the P-sampler calibrated with passive flow monitors (PFMs) and direct measurement of flow rates. The mass lost from the PFM over the deployment periods predicted water velocity to within 5.1, 0.48 and 7.1% when exposed to a flow rate pulse (7.5–50 cm s⁻¹), concentration pulse (5–100 μg P L⁻¹), or both simultaneously. For the P-sampler, good agreement was observed between the grab and passive measurements of FRP concentration when exposed to a pulse in flow (6% overestimation) or concentration (2% underestimation).
显示更多 [+] 显示较少 [-]Road deicing salt irreversibly disrupts osmoregulation of salamander egg clutches
2011
Karraker, Nancy E. | Gibbs, James P.
It has been postulated that road deicing salts are sufficiently diluted by spring rains to ameliorate any physiological impacts to amphibians breeding in wetlands near roads. We tested this conjecture by exposing clutches of the spotted salamander (Ambystoma maculatum) to three chloride concentrations (1 mg/L, 145 mg/L, 945 mg/L) for nine days, then transferred clutches to control water for nine days, and measured change in mass at three-day intervals. We measured mass change because water uptake by clutches reduces risks to embryos associated with freezing, predation, and disease. Clutches in controls sequestered water asymptotically. Those in the moderate concentrations lost 18% mass initially and regained 14% after transfer to control water. Clutches in high concentration lost 33% mass and then lost an additional 8% after transfer. Our results suggest that spring rains do not ameliorate the effects of deicing salts in wetlands with extremely high chloride concentrations.
显示更多 [+] 显示较少 [-]Toxic effects of oral 2-amino-4,6-dinitrotoluene in the Western fence lizard (Sceloporus occidentalis)
2011
McFarland, Craig A. | Quinn, Michael J., Jr | Boyce, John | LaFiandra, Emily M. | Bazar, Matthew A. | Talent, Larry G. | Johnson, Mark S.
The compound 2-amino-4,6-dinitrotoluene (2A-DNT) was evaluated under laboratory conditions in the Western fence lizard (Sceloporus occidentalis) to assess the potential for reptile toxicity. Oral LD₅₀ values were 1406 and 1867 mg/kg for male and female lizards, respectively. Based on responses from a 14-day subacute study, a 60-day subchronic experiment followed where lizards were orally dosed at 0, 5, 15, 20, 25, 30 mg/kg-d. At day 60, number of days and survivors, food consumption, and change in body weight were inversely related to dose. Signs of toxicity were characterized by anorexia and generalized cachexia. Significant adverse histopathology was observed in hepatic tissue at ≥15 mg/kg-d, consistent with hepatocellular transdifferentiation. Based on survival, loss of body weight, diminished food intake, changes in liver, kidney, and testes, and increased blood urea nitrogen, these data suggest a LOAEL of 15 mg/kg-d and a NOAEL of 5 mg/kg-d in S. occidentalis.
显示更多 [+] 显示较少 [-]Quantification of centimeter-scale spatial variation in PAH, glucose and benzoic acid mineralization and soil organic matter in road-side soil
2011
Hybholt, Trine K. | Aamand, Jens | Johnsen, Anders R.
The aim of the study was to determine centimeter-scale spatial variation in mineralization potential in diffusely polluted soil. To this end we employed a 96-well microplate method to measure the mineralization of ¹⁴C-labeled organic compounds in deep-well microplates and thereby compile mineralization curves for 348 soil samples of 0.2-cm³. Centimeter-scale spatial variation in organic matter and the mineralization of glucose, benzoic acid, and PAHs (phenanthrene and pyrene) was determined for urban road-side soil sampled as arrays (7×11cm) of 96 subsamples. The spatial variation in mineralization was visualized by means of 2-D contour maps and quantified by means of semivariograms. The geostatistical analysis showed that the easily degradable compounds (glucose and benzoic acid) exhibited little spatial variation in mineralization potential, whereas the mineralization was highly heterogeneous for the PAH compounds that require specialized degraders. The spatial heterogeneity should be taken into account when estimating natural attenuation rates.
显示更多 [+] 显示较少 [-]Spatial and temporal variability in urban fine particulate matter concentrations
2011
Levy, Jonathan I. | Hanna, Steven R.
Identification of hot spots for urban fine particulate matter (PM₂.₅) concentrations is complicated by the significant contributions from regional atmospheric transport and the dependence of spatial and temporal variability on averaging time. We focus on PM₂.₅ patterns in New York City, which includes significant local sources, street canyons, and upwind contributions to concentrations. A literature synthesis demonstrates that long-term (e.g., one-year) average PM₂.₅ concentrations at a small number of widely-distributed monitoring sites would not show substantial variability, whereas short-term (e.g., 1-h) average measurements with high spatial density would show significant variability. Statistical analyses of ambient monitoring data as a function of wind speed and direction reinforce the significance of regional transport but show evidence of local contributions. We conclude that current monitor siting may not adequately capture PM₂.₅ variability in an urban area, especially in a mega-city, reinforcing the necessity of dispersion modeling and methods for analyzing high-resolution monitoring observations.
显示更多 [+] 显示较少 [-]Metabolic responses of Eisenia fetida after sub-lethal exposure to organic contaminants with different toxic modes of action
2011
McKelvie, Jennifer R. | Wolfe, David M. | Celejewski, Magda A. | Alaee, M. (Mehran) | Simpson, Andre J. | Simpson, Myrna J.
Nuclear magnetic resonance (NMR) – based metabolomics has the potential to identify toxic responses of contaminants within a mixture in contaminated soil. This study evaluated the metabolic response of Eisenia fetida after exposure to an array of organic compounds to determine whether contaminant-specific responses could be identified. The compounds investigated in contact tests included: two pesticides (carbaryl and chlorpyrifos), three pharmaceuticals (carbamazephine, estrone and caffeine), two persistent organohalogens (Aroclor 1254 and PBDE 209) and two industrial compounds (nonylphenol and dimethyl phthalate). Control and contaminant-exposed metabolic profiles were distinguished using principal component analysis and potential contaminant-specific biomarkers of exposure were found for several contaminants. These results suggest that NMR-based metabolomics offers considerable promise for differentiating between the different toxic modes of action (MOA) associated with sub-lethal toxicity to earthworms.
显示更多 [+] 显示较少 [-]Sediment quality guidelines for copper and zinc for filter-feeding estuarine oysters?
2011
Birch, G.F. | Hogg, T.D.
Sediment quality guidelines (SQGs) assess the ability of bottom sediment to sustain healthy infauna and water quality guidelines (WQGs) provide protection for a designated percentage of aquatic species. Filter-feeding marine species, e.g. oysters and mussels, acquire food from particles in the water column and protection of these animals is not provided by SQGs or WQGs. The current work investigated the relationship between metal (Cu, Zn) concentrations in total and fine-fraction (<62.5μm) surficial sediment digested in a range of acids and chelating agents and oyster tissue metal concentrations. A strong correlation between oyster tissue Cu and Zn concentrations and fine-fraction surficial sediment digested in 1M HCl provided a sedimentary guideline which predicted tissue metal concentrations in oysters and established a level (<45μgg⁻¹ and <1000μgg⁻¹, respectively) for protecting oysters from exceeding human consumption levels (70μgg⁻¹ and 1000μgg⁻¹, respectively).
显示更多 [+] 显示较少 [-]A rapidly equilibrating, thin film, passive water sampler for organic contaminants; characterization and field testing
2011
St. George, Tiffany | Vlahos, Penny | Harner, Tom | Helm, Paul | Wilford, Bryony
Improving methods for assessing the spatial and temporal resolution of organic compound concentrations in marine environments is important to the sustainable management of our coastal systems. Here we evaluate the use of ethylene vinyl acetate (EVA) as a candidate polymer for thin-film passive sampling in waters of marine environments. Log KEVA₋W partition coefficients correlate well (r² = 0.87) with Log KOW values for selected pesticides and polychlorinated biphenyls (PCBs) where Log KEVA₋W = 1.04 Log KOW + 0.22. EVA is a suitable polymer for passive sampling due to both its high affinity for organic compounds and its ease of coating at sub-micron film thicknesses on various substrates. Twelve-day field deployments were effective in detecting target compounds with good precision making EVA a potential multi-media fugacity meter.
显示更多 [+] 显示较少 [-]Detection of fullerenes (C₆₀ and C₇₀) in commercial cosmetics
2011
Benn, Troy M. | Westerhoff, Paul | Herckes, Pierre
Detection methods are necessary to quantify fullerenes in commercial applications to provide potential exposure levels for future risk assessments of fullerene technologies. The fullerene concentrations of five cosmetic products were evaluated using liquid chromatography with mass spectrometry to separate and specifically detect C₆₀ and C₇₀ from interfering cosmetic substances (e.g., castor oil). A cosmetic formulation was characterized with transmission electron microscopy, which confirmed that polyvinylpyrrolidone encapsulated C₆₀. Liquid-liquid extraction of fullerenes from control samples approached 100% while solid-phase and sonication in toluene extractions yielded recoveries of 27–42%. C₆₀ was detected in four commercial cosmetics ranging from 0.04 to 1.1 μg/g, and C₇₀ was qualitatively detected in two samples. A single-use quantity of cosmetic (0.5 g) may contain up to 0.6 μg of C₆₀, demonstrating a pathway for human exposure. Steady-state modeling of fullerene adsorption to biosolids is used to discuss potential environmental releases from wastewater treatment systems.
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