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In an intensive subcontimental study of pesticides in surface waters of the United States, concentrations of 26 high-use pesticides were measured at nine sites in the Mississippi River basin from May 1991 through March 1992. Calculated total fluxes were combined with agricultural-use data to estimate the percentage of applied pesticide reaching the mouths of the Mississippi River and six major tributaries. For most pesticides, the riverine flux was less than 2% of the mass applied agriculturally. The insecticide diazinon was detected frequently in rivers draining the three basins with the highest population densities, apparently as a result of urban use.
Semipermeable membrane devices (SPMDs) were employed to sample sediment pore water in static exposure studies under controlled laboratory conditions using (control pond and formulated) sediments fortified with 15 priority pollutant polycyclic aromatic hydrocarbons (PPPAHs). The sediment fortification level of 750 ng/g was selected on the basis of what might be detected in a sediment sample from a contaminated area. The sampling interval consisted of 0, 4, 7, 14, and 28 days for each study. The analytical methodologies, as well as the extraction and sample cleanup procedures used in the isolation, characterization, and quantitation of 15 PPPAHs at different fortification levels in SPMDs, water, and sediment were...
Thirteen river waters and one humic lake water were characterized. The effects of dissolved organic matter (DOM) on the bioavailability of atrazine, pyrene and benzo[a]pyrene (B[a]P) was evaluated. Binding of the chemicals by DOM was analyzed with the equilibrium dialysis technique. For each of the water samples, 24 h bioconcentration factors (BCFs) of the chemicals were measured in Daphnia magna. The relationship between DOM and other water characteristics (including conductivity, water hardness and pH), and bioavailability of the chemicals was studied by performing several statistical analyses, including multiple regression analyses, to determine how much of the variation of BCF values could be explained by the...
Adult rare minnow (Gobiocypris rarus) were exposed to 0, 1, 5, and 25 ng/l (nominal concentrations) of 17α-ethynylestradiol (EE2) and 3, 10, and 30 μg/l (nominal concentrations) of 4-nonylphenol (NP) under flow-through conditions for a period of 28 d. Low mortality was observed at 5 and 25 ng/l EE2 and the growth of fish reduced significantly at 25 ng/l EE2 compared to controls. However, the gonadosomatic indices (GSI) of male fish were significantly higher in 1 ng/l EE2 treatments and in 10 and 30 μg/l NP treatments (p < 0.05). Renal somatic indices (RSI) of male fish in EE2 treatments were significantly higher than those in controls (p < 0.05). In contrast, significantly decreased GSI and RSI of female fish could...
Coal-tar-based pavement sealants, a major source of PAHs to urban water bodies, are a potential source of volatile PAHs to the atmosphere. An initial assessment of volatilization of PAHs from coal-tar-sealed pavement is presented here in which we measured summertime gas-phase PAH concentrations 0.03 m and 1.28 m above the pavement surface of seven sealed (six with coal-tar-based sealant and one with asphalt-based sealant) and three unsealed (two asphalt and one concrete) parking lots in central Texas. PAHs also were measured in parking lot dust. The geometric mean concentration of the sum of eight frequently detected PAHs (ΣPAH8) in the 0.03-m samples above sealed lots (1320 ng m-3) during the hottest part of the...
Archived soil samples can provide important information on the history of environmental contamination and by comparison with recently collected samples, temporal trends can be inferred. Little previous work has addressed whether mercury (Hg) concentrations in soil samples are stable with long-term storage under standard laboratory conditions. In this study, we have re-analyzed using cold vapor atomic adsorption spectroscopy a set of archived soil samples that ranged from relatively pristine mountainous sites to a polluted site near a non-ferrous metal smelter with a wide range of Hg concentrations (6 - 6485 µg kg-1). Samples included organic and mineral soils and peats with a carbon content that ranged from 0.2...
Large N2O emissions were observed from intertidal sediments in a coastal estuary, West Falmouth Harbor, MA, USA. Average N2O emission rates from 41 chambers during summer 2008 were 10.7 mol N2O m(-2) h(-1)±4.43 μmol N2O m(-2) h(-1) (standard error). Emissions were highest from sediments within a known wastewater plume, where a maximum N2O emission rate was 155 μmol N2O m(-2) h(-1). Intertidal N2O fluxes were positively related to porewater ammonium concentrations at 10 and 25 cm depths. In groundwater from 7 shoreline wells, dissolved N2O ranged from 488% of saturation (56 nM N2O) to more than 13000% of saturation (1529 nM N2O) and was positively related to nitrate concentrations. Fresh and brackish porewater underlying...
Seasonal trends of benthic methylmercury (methyl-Hg) production were examined in both littoral and open water sites of three lakes (Escondido, Moreno, and Morenito) in the North Andean Patagonia region of Argentina. Potentials of methyl-Hg production were measured by amending sediment samples with inorganic 197Hg(II), incubating for either 24 and 32 h at room temperature, and subsequently assaying the radiolabelled organomercury produced. Seasonal variations of benthic methyl-Hg production were studied but no significant correlation was observed. Lake littoral sites exhibited up to two fold higher methyl-Hg production potentials in most cases. Sediment from lakes Moreno and Morenito generally exhibited much lower...
Coarse (whole) and finely ground Ambersorb 1500 and coarse and fine coconut charcoal were compared as to their efficiencies in scavenging organic contaminants desorbed from sediment. Aqueous slurries of a test sediment spiked (1 ppm) with p,p???-DDE (DDE), 2,2???,5,5???-tetrachlorobiphenyl (TCB), naphthalene (NAP), or phenanthrene (PHEN), and containing 1% levels of the test carbons were treated by shaking at 35 ??C while exposed to clusters of low-density polyethylene membrane (detox spiders). Controls consisted of spiked sediments and detox spiders but no added carbon of any kind and thus represented unimpeded bioavailabilities (to the spiders). After the treatments - agitation periods from 2.5 to 60 h, depending...
Photolysis of rhodamine-WT dye under natural sunlight conditions was determined by measuring the loss of fluorescence as a function of time. Rate coefficients at 30?? north latitude ranged from 4.77 x 10-2 day-1 for summer to 3.16 x 10-2 day-1 for winter. Experimental coefficients were in good agreement with values calculated using a laboratory-determined value of the quantum yield.
A heated purge-and-trap gas chromatography/mass spectrometry method was used to determine the cis- and trans-isomers of (4-methylcyclohexyl)methanol (4-MCHM), the reported major component of the Crude MCHM/Dowanol™ PPh glycol ether material spilled into the Elk River upriver from Charleston, West Virginia, on January 9, 2014. The trans-isomer eluted first and method detection limits were 0.16-μg L−1trans-, 0.28-μg L−1cis-, and 0.4-μg L−1 Total (total response of isomers) 4-MCHM. Estimated concentrations in the spill source material were 491-g L−1trans- and 277-g L−1cis-4-MCHM, the sum constituting 84% of the source material assuming its density equaled 4-MCHM. Elk River samples collected ⩽ 3.2 km downriver from...
The use of dilutions has been the foundation of our approach for assessing contaminated water, and accordingly, it may be important to establish similar or parallel approaches for sediment dilutions. Test organism responses to dilution gradients can identify the degree of necessary sediment alteration to reduce the toxicity. Using whole sediment dilutions to represent the complex interactions of in situ sediments can identify the toxicity, but the selection of the appropriate diluent for the contaminated sediment may affect the results and conclusions drawn. Contaminated whole sediments were examined to evaluate the toxicity of dilutions of sediments with a diversity of test organisms. Dilutions of the contaminated...
The semipermeable membrane device (SPMD), consisting of a neutral lipid (triolein) enclosed in polyethylene layflat tubing, is demonstrated to be a highly efficient passive air sampler. These devices readily sequester lipophilic organic contaminants from the vapor phase. Specifically, the SPMDs are shown to concentrate polychlorinated biphenyl (PCB) residues from a laboratory atmosphere in a linear manner through 28 days. Under the conditions of this study, a three device composite (1.4 g triolein) extracted PCB residues from ≈ 7 m3 of air per day.
The Rybinsk Reservoir (Russia) is the largest artificial waterbody in Europe (4550 km2) and provides drinking water for population of the cities located along the coast line. Industrialization in Cherepovets at the northeastern portion of the reservoir, including one of the largest metallurgical facilities in Europe, has resulted in chemical contamination of the reservoir. The extent of polychlorinated biphenyls (PCB) contamination in bream liver, a common fish species, taken from six locations in the Rybinsk Reservoir and Volga River, and biochemical and morphometric biomarkers of fish health were investigated. Liver PCB concentrations ranged from non-detected to 3.4 μg/g wet wt of liver, with the greatest concentrations...
A rat hepatoma cell line, H4IIE serves as a bioassay tool to assess the potential toxicity of dioxin-like chemicals, including polychlorinated biphenyls (PCB) in environmental samples. PCB exposure to these cells induces cytochrome (CYP) P4501A1 activity in a dose-dependent fashion, thus allowing assessment of mixtures. The objective of this study was to determine the effect of different carriers, dimethyl sulfoxide (DMSO) and isooctane on the concentrations of PCBs in the H411E cells and induction of CYPIA1 activity as measured by ethoxyresorufm O-deethylase (EROD) activity. H4IIE cells were dosed with three micrograms of UL-14C-PCB77/ plate dissolved in DMSO or isooctane, and were harvested at sequential time...
Soil redox potential (Eh), concentrations of oxygen (O2) and three greenhouse gases (CO2, CH4, and N2O) were measured in the soil profile of a coastal forest at ridge, transition, and swamp across a hydrological gradient. The results delineated a distinct boundary in soil Eh and O2 concentration between the ridge and swamp with essentially no overlap between the two locations. Critical soil Eh to initiate significant CH4 production under this field conditions was about +300 mV, much higher than in the homogenous soils (about -150 mV). The strength of CH4 source to the atmosphere was strong for the swamp, minor for the transition, and negligible or even negative (consumption) for the ridge. Maximum N2O concentration...
The semipermeable membrane device (SPMD), consisting of a neutral lipid (triolein) enclosed in polyethylene layflat tubing, is very effective in sequestering bioavailable organochlorine (OC) pesticides in the environment. We used SPMDs to sequester OC pesticide residues in streams receiving irrigation drainwater and found toxaphene, the DDT complex, dieldrin, and endrin. Ambient water concentrations of the OC pesticides were calculated using an algorithm developed previously. Toxaphene residues were estimated to range from 300 to 7,000 ng/L.
Volatilization fluxes of seven ketones were measured over a range of temperatures. Gas-film coefficients were calculated from these volatilization fluxes and related to the gas-film coefficient for the evaporation of water. These relations, when combined with an equation for estimating the gas-film coefficient for evaporation of water from a canal, permit estimating gas-film coefficients for the volatilization of ketones from streams and rivers.
Large amounts of the 'fuel-oxygenate' compound methyl-tert-butyl ether (MTBE) are currently being used in gasoline to reduce carbon monoxide and ozone in urban air and to boost fuel octane. Because MTBE can be transported to surface waters in various ways, established theory was used to calculate half-lives for MTBE volatilizing from flowing surface waters. Similar calculations were made for benzene as a representative of the 'BTEX' group of compounds (benzene, toluene, ethyl benzene, and the xylenes), and for tert-butyl alcohol (TBA). The calculations were made as a function of the mean flow velocity u (m/day), the mean flow depth h (m), the ambient temperature, and the wind speed. In deep, slow-moving flows, MTBE...
The stereoisomers of metolachlor and its two polar metabolites [ethane sulfonic acid (ESA) and oxanilic acid (OXA)] were separated using liquid chromatography–mass spectrometry (LC–MS) and capillary zone electrophoresis (CZE), respectively. The separation of metolachlor enantiomers was achieved using a LC–MS equipped with a chiral stationary phase based on cellulose tris(3,5-dimethylphenyl carbamate) and an atmospheric pressure chemical ionization source operated under positive ion mode. The enantiomers of ESA and OXA were separated using CZE with gamma-cyclodextrin (γ-CD) as chiral selector. Various CZE conditions were investigated to achieve the best resolution of the ESA and OXA enantiomers. The optimum background...
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