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ABSTRACT: Evaluation of dredged material for aquatic placement requires assessment of bioaccumulation potentials for benthic organisms using standardized laboratory bioaccumulation tests. Critical to the interpretation of these data is the assessment of steady state for bioaccumulated residues needed to generate biota sediment accumulation factors (BSAFs) and to address control correction of day 0 contaminant residues measured in bioassay organisms. This study applied a novel performance reference compound approach with a pulse-chase experimental design to investigate elimination of a series of isotopically labeled polychlorinated biphenyl ((13)C-PCBs) in the polychaete worm Nereis virens while simultaneously evaluating native PCB bioaccumulation from field-collected sediments. Results demonstrated that all (13)C-PCBs, with the exception of (13)C-PCB209 (> 80%), were eliminated by more than 90% after 28 d. The three sediment types yielded similar (13)C-PCB whole-body elimination rate constants (k(tot)) producing the following predictive equation: log k(tot) = - 0.09 × log K(OW) - 0.45. The rapid loss of (13)C-PCBs from worms over the bioassay period indicated that control correction, by subtracting day 0 residues, would result in underestimates of bioavailable sediment residues. Significant uptake of native PCBs was observed only in the most contaminated sediment and proceeded according to kinetic model predictions with steady-state BSAFs ranging from 1 to 3 and peaking for congeners of log K(OW) between 6.2 and 6.5. The performance reference compound approach can provide novel information about chemical toxicokinetics and also serve as a quality check for the physiological performance of the bioassay organism during standardized bioaccumulation testing.
Environmental Toxicology and Chemistry 03/2011; 30(6):1366-75. · 2.81 Impact Factor
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ABSTRACT: Methyl parathion (MeP) was introduced into constructed wetlands for the purpose of assessing the influence of emergent vegetation on transport and toxicity of the pesticide. Two vegetated (90% cover, mainly Juncus effusus) and two nonvegetated wetland cells (each with a water body of 50 × 5.5 × 0.2 m) were each dosed with 6.5 m3 of water containing active ingredient of MeP at 6.6 mg/L associated with suspended soil at 400 mg/L to simulate a storm runoff event. Acute toxicity was assessed by sampling benthic macroinvertebrates at 5, 10, 20, and 40 m from the inlet before and 96 h after contamination and by in situ exposure of Chironomus tentans (Diptera) up to 24 h after contamination. Methyl parathion was detected throughout the nonvegetated wetland cells (70 μg/L at 20 m, 8 μg/L at 40 m), whereas the pesticide was not transported through the vegetated wetland cells (20 μg/L at 20 m, <0.1 μg/L at 40 m). A three-way analysis of variance using contamination (repeated measure variable), location, and vegetation indicated significant negative effects of contamination on various insect taxa, such as mayfly nymphs and caddisfly larvae. Seven out of the total of 15 species revealed a significant contamination × vegetation effect, with individuals in the vegetated wetlands being less affected. Four species showed a significant contamination × location effect, confirming a higher toxicity in the inlet area of the wetlands. A significant three-way interaction of contamination × vegetation × location was detected in Chironomus sp., which was most strongly affected at the inlet area of the nonvegetated wetland cells. The in situ bioassay employing C. tentans confirmed the positive effect of wetland vegetation on MeP toxicity. These results demonstrate the importance of vegetation for pesticide mitigation in constructed wetlands.
Environmental Toxicology and Chemistry 11/2009; 22(6):1262 - 1268. · 2.81 Impact Factor
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ABSTRACT: Alkylphenol polyethoxylates are a major class of nonionic surfactants that are microbially degraded in sewage treatment plants (STPs) and sediments to more toxic and hydrophobic alkylphenols. Recent data on the estrogenic activity of alkylphenols has prompted interest in the distribution of these compounds in the aquatic environment. Sediment samples were collected from several sites (n = 28) at industrialized and pristine regions of Lake Huron, Lake Erie, and Lake Ontario, USA and Canada, and analyzed for concentrations of 4-nonylphenol (NP) and 4-(tert)-octylphenol (OP). Also, sludge samples were taken from a secondary STP in Whitby, Ontario, Canada. Sediment and sludge samples and analytical standards were prepared for analysis by gas chromatography–mass spectrometry in selected ion mode by combined acetylation and supercritical fluid extraction. Concentrations of NP were up to 37 μg/g in sediments and >300 μg/g in the sewage sludge. Concentrations of OP were up to 23 μg/g in sediment and 21 μg/g in the sewage sludge. These data indicate that alkylphenols are distributed widely in sediments in the lower Great Lakes. However, concentrations of NP were present at high (μg/g) levels only in sediments near urban and industrialized centers.
Environmental Toxicology and Chemistry 11/2009; 17(7):1230 - 1235. · 2.81 Impact Factor
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ABSTRACT: Degradation of alkylphenol ethoxylate (APEO) surfactants in the environment leads to the formation of relatively hydrophobic compounds such as nonylphenol (NP), octylphenol (OP), nonylphenol monoethoxylate (NP1EO), and nonylphenol diethoxylate (NP2EO) that have been shown to have estrogenic activity. Previous studies have shown that sewage treatment plants (STPs) are point sources for these compounds in the aquatic environment. We collected sediment samples at several sites in the vicinity of STPs in Hamilton Harbour and in the Detroit River to determine the spatial distribution of the degradation products of APEOs. In addition, we deployed semipermeable membrane devices (SPMDs) and caged freshwater mussels (Elliptio complanata) at these locations to determine the distribution of these compounds in the dissolved phase and their potential to bioaccumulate in aquatic organisms. The NP, OP, NP1EO, and NP2EO were found at μg/g (dry wt.) concentrations in sediments and accumulated to ng/g (wet wt.) concentrations in caged mussels near the STPs. However, in the Detroit River, the concentrations of these compounds declined to near background levels in the sediments, water column (i.e., SPMDs), and biota at stations about 1 km downstream from STPs. At stations in Hamilton Harbour, concentrations of APEO degradation products also declined markedly in sediments and SPMDs located a few hundred meters from the STP. These data indicate that degradation products of APEOs can be accumulated by biota near STPs. However, the environmental distribution of these compounds is localized to areas close to the point of discharge.
Environmental Toxicology and Chemistry 11/2009; 19(4):784 - 792. · 2.81 Impact Factor
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Marine pollution bulletin 06/2009; 58(7):1078-83. · 2.63 Impact Factor
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ABSTRACT: The influence of seasonal changes in water conditions and parameters on several major pharmacologically active compounds (PhACs) and s-triazine herbicides was assessed in the wastewater and sewage treatment plant (WSTP) effluent as well as the downstream surface water from sites on the Canadian side of the upper Detroit River, between the Little River WSTP and near the water intake of a major drinking water treatment facility for the City of Windsor (ON, Canada). The assessed PhACs were of neutral (carbamazepine, cotinine, caffeine, cyclophosphamide, fluoxetine, norfluoxetine, pentoxifylline, and trimethoprim) and acidic (ibuprofen, bezafibrate, clofibric acid, diclofenac, fenoprofen, gemfibrozil, indomethacin, naproxen, and ketoprofen) varieties. The major assessed s-triazine herbicides were atrazine, simazine, propazine, prometon, ametryn, prometryn, and terbutryn. At sampling times from September 2002 to June 2003, 15 PhACs were detected in the WSTP effluent at concentrations ranging from 1.7 to 1244 ng/L. The PhAC concentrations decreased by as much 92 to 100% at the Little River/Detroit River confluence because of the river dilution effect, with further continual decreases at sites downstream from the WSTP. The only quantifiable s-triazine in WSTP effluent, atrazine, ranged from 6.7 to 200 ng/L and was higher in Detroit River surface waters than in WSTP effluent. Only carbamazepine, cotinine, and atrazine were detectable at the low-nanogram and subnanogram levels in surface waters near a drinking water intake site. Unlike the PhACs, atrazine in the Detroit River is not attributable to point sources, and it is heavily influenced by seasonal agricultural usage and runoff. Detroit River surface water concentrations of carbamazepine, cotinine, and atrazine may present a health concern to aquatic wildlife and to humans via the consumption of drinking water.
Environmental Toxicology and Chemistry 10/2006; 25(9):2356-65. · 2.81 Impact Factor
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ABSTRACT: The depletion and degradation of pharmacologically active compounds (PhACs) and pesticides as a function of ozonation in drinking water treatment processes is not well studied. The A.H. Weeks drinking water treatment plant (DWTP) serves the City of Windsor, Ontario Canada, and incorporates ozone treatment into the production of drinking water. This DWTP also operates a real-time, scaled down pilot plant, which has two parallel streams, conventional and ozone plus conventional treatments. In this study water samples were collected from key points in the two streams of the pilot plant system to determine the depletion and influence of seasonal changes in water processing parameters on eighteen major PhACs (and metabolites) and seven s-triazines herbicides. However, only carbamazepine (antiepileptic), caffeine (stimulant), cotinine (metabolite of nicotine) and atrazine were consistently detectable in the raw water intake (low to sub-ng/L level). Regardless of the seasonality, the flocculation-coagulation and dual media filtration steps without ozone treatment resulted in no decrease in analyte concentrations, while decreases of 66-100% (undetectable, method detection limits 0.05-1 ng/L) of the analyte concentrations were observed when ozone treatment was part of the water processing. These findings demonstrate that ozone treatment is highly effective in depleting carbamazepine, caffeine, cotinine, and atrazine, and thus is highly influential in the fate of these compounds in drinking water treatment regardless of the seasonal time frame. Currently very few Canadian DWTPs incorporate ozonation into conventional treatment, which suggests that human exposure to these compounds via drinking water consumption may be an issue in affected communities.
Water Research 08/2006; 40(12):2259-66. · 4.86 Impact Factor
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ABSTRACT: Drainage ditches are indispensable components of the agricultural production landscape. A benefit of these ditches is contaminant mitigation of agricultural storm runoff. This study determined bifenthrin and lambda-cyhalothrin (two pyrethroid insecticides) partitioning and retention in ditch water, sediment, and plant material as well as estimated necessary ditch length required for effective mitigation. A controlled-release runoff simulation was conducted on a 650-m vegetated drainage ditch in the Mississippi Delta, USA. Bifenthrin and lambda-cyhalothrin were released into the ditch in a water-sediment slurry. Samples of water, sediment, and plants were collected and analyzed for pyrethroid concentrations. Three hours following runoff initiation, inlet bifenthrin and lambda-cyhalothrin water concentrations ranged from 666 and 374 microg/L, respectively, to 7.24 and 5.23 microg/L at 200 m downstream. No chemical residues were detected at the 400-m sampling site. A similar trend was observed throughout the first 7 d of the study where water concentrations were elevated at the front end of the ditch (0-25 m) and greatly reduced by the 400-m sampling site. Regression formulas predicted that bifenthrin and lambda-cyhalothrin concentrations in ditch water were reduced to 0.1% of the initial value within 280 m. Mass balance calculations determined that ditch plants were the major sink and/or sorption site responsible for the rapid aqueous pyrethroid dissipation. By incorporating vegetated drainage ditches into a watershed management program, agriculture can continue to decrease potential non-point source threats to downstream aquatic receiving systems. Overall results of this study illustrate that aquatic macrophytes play an important role in the retention and distribution of pyrethroids in vegetated agricultural drainage ditches.
Environmental Toxicology and Chemistry 10/2005; 24(9):2121-7. · 2.81 Impact Factor
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ABSTRACT: Triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol) is an antimicroibial disinfectant agent used in a wide array of consumer products. An analytical method based on solid-phase extraction (SPE) followed by reverse phase, liquid chromatography coupled with electrospray ionization (negative)-tandem quadrupole mass spectrometry (LC-ESI(-)-MS/MS; in the multiple reaction monitoring (MRM) mode) was developed, optimized and validated for the determination of triclosan in wastewater/sewage treatment plant (WSTP) effluent and surface waters from the upper Detroit River (Canada). The mean recoveries (+/-%RSD) of triclosan and the internal standard 2'-HO-tribromodiphenyl ether (2'-HO-BDE-28) spiked to surface water and WSTP effluent samples ranged similarly from 104+/-8% and 91+/-10%, respectively, and method limits of quantification were in the low ppb/high ppt range. However, ESI(-) enhancement was found for both analytes due to sample matrix effects, as indicated by % process efficiencies (a measure of ESI(-) enhancement/suppression), which were in the 111-128% range. We report the first known assessment of triclosan in the Detroit River watershed of the Great Lakes, which preliminarily examined the presence and UV-treatment effects on triclosan in effluent from the major WSTP serving the City of Windsor, Ontario, Canada, and fate in surface waters of the upper Detroit River. Triclosan in WSTP effluent decreased 22% after final UV treatment to a mean concentration of 63 ng/L. Concentrations were further reduced to 4 and 8 ng/L (a >90% reduction) in surface water samples from sites downstream on the Canadian shoreline of the Detroit River, which was due to dilution. Two hydroxylated tribrominated diphenyl ethers, which are structurally similar to triclosan, were also detected in WSTP effluent and surface water samples.
Environment International 07/2005; 31(5):621-30. · 5.30 Impact Factor
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ABSTRACT: Methyl parathion (MeP) was introduced into constructed wetlands for the purpose of assessing the influence of emergent vegetation on transport and toxicity of the pesticide. Two vegetated (90% cover, mainly Juncus effusus) and two nonvegetated wetland cells (each with a water body of 50 x 5.5 x 0.2 m) were each dosed with 6.5 m3 of water containing active ingredient of MeP at 6.6 mg/L associated with suspended soil at 400 mg/L to simulate a storm runoff event. Acute toxicity was assessed by sampling benthic macroinvertebrates at 5, 10, 20, and 40 m from the inlet before and 96 h after contamination and by in situ exposure of Chironomus tentans (Diptera) up to 24 h after contamination. Methyl parathion was detected throughout the nonvegetated wetland cells (70 microg/L at 20 m, 8 microg/L at 40 m), whereas the pesticide was not transported through the vegetated wetland cells (20 microg/L at 20 m, < 0.1 microg/L at 40 m). A three-way analysis of variance using contamination (repeated measure variable), location, and vegetation indicated significant negative effects of contamination on various insect taxa, such as mayfly nymphs and caddisfly larvae. Seven out of the total of 15 species revealed a significant contamination x vegetation effect, with individuals in the vegetated wetlands being less affected. Four species showed a significant contamination x location effect, confirming a higher toxicity in the inlet area of the wetlands. A significant three-way interaction of contamination x vegetation x location was detected in Chironomus sp., which was most strongly affected at the inlet area of the nonvegetated wetland cells. The in situ bioassay employing C. tentans confirmed the positive effect of wetland vegetation on MeP toxicity. These results demonstrate the importance of vegetation for pesticide mitigation in constructed wetlands.
Environmental Toxicology and Chemistry 07/2003; 22(6):1262-8. · 2.81 Impact Factor
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ABSTRACT: Our knowledge about the effectiveness of constructed wetlands in retaining agricultural nonpoint-source pesticide pollution is limited. A 0.44-ha vegetated wetland built along a tributary of the Lourens River, Western Cape, South Africa, was studied to ascertain the retention, fate, and effects of spray drift-borne azinphos-methyl (AZP). Composite water samples taken at the inlet and outlet during five spray drift trials in summer 2000 and 2001 revealed an overall reduction of AZP levels by 90 +/- 1% and a retention of AZP mass by 61 +/- 5%. Samples were collected at the inlet outlet, and four platforms within the wetland to determine the fate and effect of AZP in the wetland after direct spray drift deposition in the tributary 200 m upstream of the inlet. Peak concentrations of AZP decreased, and the duration of exposure increased from inlet (0.73 microg/L; 9 h) via platforms 1 and 4 to outlet (0.08 microg/L; 16 h). AZP sorbed to plants or plant surfaces, leading to a peak concentration of 6.8 microg/kg dw. The living plant biomass accounted for 10.5% of the AZP mass initially retained in the wetland, indicating processes such as volatilization, photolysis, hydrolysis, or metabolic degradation as being very important AZP was not detected in sediments. Water samples taken along two 10-m transects situated perpendicular to the shore indicated a homogeneous horizontal distribution of the pesticide: 0.23 +/- 0.02 and 0.14 +/- 0.04 microg/L (n = 5), respectively. Both Copepoda (p = 0.019) and Cladocere (p = 0.027) decreased significantly 6 h postdeposition and remained at reduced densities for at least 7 d. In parallel, the chlorophyll a concentration showed an increase, although not significant, within 6 h of spray deposition. The study highlights the potential of constructed wetlands as a risk-mitigation strategy for spray drift-related pesticide pollution.
Environmental Science and Technology 06/2003; 37(10):2139-44. · 5.23 Impact Factor
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