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At least 757 records · Page 42Linked to original sources
USGS1995

Dietary exposure of mink to carp from Saginaw Bay. 3. Characterization of dietary exposure to planar halogenated hydrocarbons, dioxin equivalents, and biomagnification

Mink are known to be very sensitive to the toxic effects of planar polychlorinated biphenyls (pPCBs), polychlorinated dibenzo- p -dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs), collectively known as planar halogenated hydrocarbons (PHHs). Previously, we reported the reproductive effects in mink fed a diet containing 10, 20, or 40% fish taken from Saginaw Bay, Lake Huron. The present study reports the chemical characterization of the diets and the adult mink livers, along with a comparison of an additive model of toxicity with the results of the H4IIE bioassay on these samples. The assessment of dietary or tissue-based exposure of the mink to 2,3,7,8-tetrachlorodibenzo- p -dioxin (TCDD) and related compounds revealed that TCDD equivalents of the PHH mixtures largely followed an additive model of toxicity as compared with the H4IIE bioassay. Consistent dietary and liver tissue-based threshold concentrations for reproductive toxicity in mink were determined regardless of whether PHHs were quantified as TEQs (additive toxicity) or TCDD-EQs (H4IIE bioassay). Significant reproductive effects were observed in the lowest treatment group (10% fish or 19.4 pg of H4IIE bioassay-derived TCDD-EQs/g). Consumption-normalized mink liver biomagnification factors (BMFs) were 6.4−74.2 for PCDDs, <1−75.8 for PCDFs, <1−15.9 for PCBs, and in general, increased with degree of chlorination within each class. Based on TEQs or TCDD-EQ, this study confirms that mink are among the most, if not the most, sensitive mammalian species to the reproductive toxicity of TCDD and related compounds.

Environmental Science & Technology↗
USGS1996

Acetochlor in the hydrologic system in the midwestern United States, 1994

The herbicide acetochlor [2-chloro- N -(ethoxymethyl)- N -(2-ethyl-6-methylphenyl)acetamide] was given conditional registration in the United States by the U.S. Environmental Protection Agency in March 1994. This registration provided a rare opportunity to investigate the occurrence of a pesticide during its first season of extensive use in the midwestern United States. Water samples collected and analyzed by the U.S. Geological Survey during 1994 documented the distribution of acetochlor in the hydrologic system; it was detected in 29% of the rain samples from four sites in Iowa, 17% of the stream samples from 51 sites across nine states, and 0% of the groundwater samples from 38 wells across eight states. Acetochlor exhibited concentration increases in rain and streams following its application to corn in the midwestern United States, with 75% of the rainwater and 35% of the stream samples having acetochlor detected during this time period. Acetochlor concentrations in rain decreased as the growing season progressed. Based on the limited data collected for this study, it is anticipated that acetochlor concentrations will have a seasonal pattern in rain and streams similar to those of other acetanilide herbicides examined. Possible explanations for the absence of acetochlor in groundwater for this study include the rapid degradation of acetochlor in the soil zone, insufficient time for this first extensive use of acetochlor to have reached the aquifers sampled, and the possible lack of acetochlor use in the recharge areas for the wells examined.

Environmental Science & Technology↗
USGS1996

Occurrence of alachlor and its sulfonated metabolite in rivers and reservoirs of the midwestern United States: The importance of sulfonation in the transport of chloroacetanilide herbicides

Alachlor and its metabolite, 2-[(2',6'-diethylphenyl)- (methoxymethyl)amino]-2-oxoethanesulfonate (ESA), were identified in 76 reservoirs in the midwestern United States using immunoassay, liquid chromatography, and gas chromatography/mass spectrometry. The median concentration of ESA (0.48 ??g/L) exceeded the median concentration of alachlor (<0.05 ??g/L), with highest values in the upper Midwest. ESA also was detected in the Mississippi River from the mouth to the headwaters at concentrations of 0.2-1.5 ??g/L, exceeding the concentration of alachlor. In a field runoff study, alachlor rapidly formed ESA. It is hypothesized that a glutathione conjugate forms, which later oxidizes in soil to ESA. The removal of the chlorine atom lessens the toxicity of the parent compound and increases runoff potential. It is hypothesized further that sulfonic acid metabolites of other chloroacetanilides, including acetochlor, butachlor, metolachlor, and propachlor, also occur in surface water.

Midwest↗
USGS1996

Effects of sampling strategies on estimates of annual mean herbicide concentrations in midwestern rivers

The effects of 10 sampling strategies on estimates of annual mean concentrations of the herbicides atrazine, alachlor, and cyanazine in selected midwestern rivers were tested. The accuracy of the strategies was computed by comparing time-weighted annual mean herbicide concentrations calculated from water samples collected from 17 locations on midwestern rivers, with simulated annual mean concentrations calculated for each sampling strategy, using Monte Carlo simulations. Monthly sampling was the most accurate strategy tested. The U.S. Environmental Protection Agency requires quarterly sampling for municipalities using surface water as a source of drinking water. Due to the seasonality of herbicide occurrence and transport, quarterly sampling underestimates annual mean herbicide concentrations in over 40% of the simulations. Three of the strategies tested showed that, relative to quarterly sampling, a more accurate representation of annual mean concentrations could be obtained by sampling more frequently during spring and early summer runoff and assuming zero herbicide concentration during late summer and winter months.

Environmental Science & Technology↗
USGS1996

Pesticides in streams draining agricultural and urban areas in Colorado

A study was conducted from April 1993 through April 1994 to describe and compare the occurrence and distribution of pesticides in streams in a small agricultural and a small urban area in Colorado. Twenty-five water samples collected at least monthly at the mouths of two tributary streams of the South Plate River were analyzed for 47 pesticides. The results indicate that both agricultural and urban areas are probable sources for pesticides in streams. In the agricultural area, 30 pesticides were detected, and in the urban area, 22 pesticides were detected in one or more samples. Most often, the more frequently detected pesticides in both areas also were some of the more commonly used pesticides. In both areas, pesticide concentrations were higher during the summer (application period) with maximum concentrations generally occurring in storm runoff. The year-round detection of some pesticides in both areas at consistently low concentrations, regardless of season or streamflow volume, could indicate that these compounds persist in the shallow alluvial aquifer year-round.

Environmental Science & Technology↗
USGS1996

Identification of a new sulfonic acid metabolite of metolachlor in soil

An ethanesulfonic acid metabolite of metolachlor (metolachlor ESA) was identified in soil-sample extracts by negative-ion, fast-atom bombardment mass spectrometry (FAB-MS) and FAB tandem mass spectrometry (FAB-MS/MS). Production fragments from MS/MS analysis of the deprotonated molecular ion of metolachlor ESA in the soil extract can be reconciled with the structure of the synthesized standard. The elemental compositions of the (M - H)- ions of the metolachlor ESA standard and the soil-sample extracts were confirmed by high-resolution mass spectrometry. A dissipation study revealed that metolachlor ESA is formed in soil under field conditions corresponding to a decrease in the concentration of the parent herbicide, metolachlor. The identification of the sulfonated metabolite of metolachlor suggests that the glutathione conjugation pathway is a common detoxification pathway shared by chloroacetanilide herbicides.

Environmental Science & Technology↗
USGS1996

Denitrification and nitrogen transport in a coastal aquifer receiving wastewater discharge

Denitrification and nitrogen transport were quantified in a sandy glacial aquifer receiving wastewater from a septage-treatment facility on Cape Cod, MA. The resulting groundwater plume contained high concentrations of NO3- (32 mg of NL-1), total dissolved nitrogen (40.5 mg of N L-1), and dissolved organic carbon (1.9 mg of C L-1) and developed a central anoxic zone after 17 months of effluent discharge. Denitrifying activity was measured using four approaches throughout the major biogeochemical zones of the plume. Three approaches that maintained the structure of aquifer materials yielded comparable rates: acetylene block in intact sediment cores, 9.6 ng of N cm-3 d-1 (n = 61); in situ N2 production, 3.0 ng of N cm-3 d-1 (n = 11); and in situ NO3- depletion, 7.1 ng of N cm-3 d-1 (n = 3). In contrast, the mixing of aquifer materials using a standard slurry method yielded rates that were more than 15-fold higher (150 ng of N cm-3 d-1, n = 16) than other methods. Concentrations and ??15N of groundwater and effluent N2, NO3-, and NH4+ were consistent with the lower rates of denitrification determined by the intact-core or in situ methods. These methods and a plumewide survey of excess N2 indicate that 2-9% of the total mass of fixed nitrogen recharged to the anoxic zone of the plume was denitrified during the 34-month study period. Denitrification was limited by organic carbon (not NO3-) concentrations, as evidenced by a nitrate and carbon addition experiment, the correlation of denitrifying activity with in situ concentrations of dissolved organic carbon, and the assessments of available organic carbon in plume sediments. Carbon limitation is consistent with the observed conservative transport of 85-96% of the nitrate in the anoxic zone. Although denitrifying activity removed a significant amount (46250 kg) of fixed nitrogen during transport, the effects of aquifer denitrification on the nitrogen load to receiving ecosystems are likely to be small (<10%).

Environmental Science & Technology↗
USGS1995

Occurrence of selected pesticides and their metabolites in near-surface aquifers of the midwestern United States

The occurrence and distribution of selected pesticides and their metabolites were investigated through the collection of 837 water-quality samples from 303 wells across the Midwest. Results of this study showed that five of the six most frequently detected compounds were pesticide metabolites. Thus, it was common for a metabolite to be found more frequently in groundwater than its parent compound. The metabolite alachlor ethanesulfonic acid (alachlor-ESA; 2-[(2,6-diethylphenyl)(methoxymethyl)amino]-2-oxoethanesulfonic acid) was detected almost 10 times as frequently and at much higher concentrations than its parent compound alachlor (2-chloro-2&lsquo;,6&lsquo;-diethyl- N -(methoxymethyl)acetamide). The median detectable atrazine (2-chloro-4-ethylamino-6- isopropylamino- s -triazine) concentration was almost half that of atrazine residue (atrazine plus the two atrazine metabolites analyzed). Cyanazine amide [2-chloro-4-(1-carbamoyl-1-methylethylamino)-6-ethylamino- s -triazine] was detected almost twice as frequently as cyanazine (2-chloro-4-ethylamino-6-methylpropionitrileamino- s -triazine). Results show that information on pesticide metabolites is necessary to understand the environmental fate of pesticides. Consequently, if pesticide metabolites are not quantified, the effects of chemical use on groundwater quality would be substantially underestimated. Thus, continued research is needed to identify major degradation pathways for all pesticides and to develop analytical methods to determine their concentrations in water and other environmental media.

Environmental Science & Technology↗
USGS1996

Coliform contamination of a coastal embayment: Sources and transport pathways

Fecal bacterial contamination of nearshore waters has direct economic impacts to coastal communities through the loss of shellfisheries and restrictions of recreational uses. We conducted seasonal measurements of fecal coliform (FC) sources and transport pathways contributing to FC contamination of Buttermilk Bay, a shallow embayment adjacent to Buzzards Bay, MA. Typical of most coastal embayments, there were no direct sewage discharges (i.e., outfalls), and fecal bacteria from human, domestic animal, and wildlife pools entered open waters primarily through direct deposition or after transport through surface waters or groundwaters. Direct fecal coliform inputs to bay waters occurred primarily in winter (December-March) from waterfowl, ~33 x 1012 FC yr-1 or ~67% of the total annual loading. Effects of waterfowl inputs on bay FC densities were mitigated by their seasonality, wide distribution across the bay surface, and the apparent limited dispersal from fecal pellets. On-site disposal of sewage by septic systems was the single largest FC source in the watershed-embayment system, 460 x 1012 FC yr-1, but due to attenuation during subsurface transport only a minute fraction, < 0.006 x 1012 FC yr-1, reached bay waters (<0.01% of annual input to bay). Instead, surface water flows, via storm drains and natural streams under both wet- and dry-weather conditions, contributed the major terrestrial input, 12 x 1012 FC yr-1 (24% of annual input), all from animal sources. Since most of the surface water FC inputs were associated with periodic, short-duration rain events with discharge concentrated in nearshore zones, wet-weather flows were found to have a disproportionately high impact on nearshore FC levels. Elution of FC from shoreline deposits of decaying vegetation (wrack) comprised an additional coliform source. Both laboratory and field experiments suggest significant elution of bacteria from wrack, ~3 x 1012 FC yr-1 on a bay-wide basis (6% of annual input), primarily by periodic tidal flooding and possibly by major rain events. Release of coliforms during resuspension of subtidal sediments was estimated to be a minor source in this system (<1.5 x 1012 FC yr-1 or < 3% of annual input), primarily associated with large storm events in the fall and winter. Based upon the relative source strengths and the spatial and temporal patterns of FC input to Buttermilk Bay, it appears that management practices in similar settings should account for migratory waterfowl, but remediation efforts should focus on the redirection of stormwater runoff through the groundwater transport pathway.

Environmental Science & Technology↗
USGS1996

Limestone characterization to model damage from acidic precipitation: Effect of pore structure on mass transfer

The pore structure of Salem limestone is investigated, and conclusions regarding the effect of the pore geometry on modeling moisture and contaminant transport are discussed based on thin section petrography, scanning electron microscopy, mercury intrusion porosimetry, and nitrogen adsorption analyses. These investigations are compared to and shown to compliment permeability and capillary pressure measurements for this common building stone. Salem limestone exhibits a bimodal pore size distribution in which the larger pores provide routes for convective mass transfer of contaminants into the material and the smaller pores lead to high surface area adsorption and reaction sites. Relative permeability and capillary pressure measurements of the air/water system indicate that Salem limestone exhibits high capillarity end low effective permeability to water. Based on stone characterization, aqueous diffusion and convection are believed to be the primary transport mechanisms for pollutants in this stone. The extent of contaminant accumulation in the stone depends on the mechanism of partitioning between the aqueous and solid phases. The described characterization techniques and modeling approach can be applied to many systems of interest such as acidic damage to limestone, mass transfer of contaminants in concrete and other porous building materials, and modeling pollutant transport in subsurface moisture zones.

Environmental Science & Technology↗
USGS1996

Quantification of natural vapor fluxes of trichloroethene in the unsaturated zone at Picatinny Arsenal, New Jersey

The upward flux of trichloroethene (TCE) vapor through the unsaturated zone above a contaminated, water-table aquifer at Picatinny Arsenal, New Jersey, has been studied under natural conditions over a 12-month period. Vertical gas-phase diffusion fluxes were estimated indirectly by measuring the TCE vapor concentration gradient in the unsaturated zone and using Fick's law to calculate the flux. The total gas-phase flux (e.g., the sum of diffusion and advection fluxes) was measured directly with a vertical flux chamber (VFC). In many cases, the upward TCE vapor flux was several orders of magnitude greater than the upward TCE diffusion flux, suggesting that mechanisms other than steady-state vapor diffusion are contributing to the vertical transport of TCE vapors through the unsaturated zone. The measured total flux of TCE vapor from the subsurface to the atmosphere is approximately 50 kg/yr and is comparable in magnitude to the removal rate of TCE from the aquifer by an existing pump-and-treat system and by discharge into a nearby stream. The net upward flux of TCE is reduced significantly during a storm event, presumably due to the mass transfer of TCE from the soil gas to the infiltrating rainwater and its subsequent downward advection. Several potential problems associated with the measurement of total gas-phase fluxes are discussed.

Environmental Science & Technology↗
USGS1996

Influence of electron donor on the minimum sulfate concentration required for sulfate reduction in a petroleum hydrocarbon-contaminated aquifer

Fluctuations in the availability of electron donor (petroleum hydrocarbons) affected the competition between sulfate-reducing bacteria (SRB) and methanogenic bacteria (MB) for control of electron flow in a petroleum hydrocarbon-contaminated aquifer. The data suggest that abundant electron donor availability allowed MB to sequester a portion of the electron flow even when sulfate was present in sufficient concentrations to support sulfate reduction. For example, in an area of abundant electron-donor availability, SRB appeared to be unable to sequester the electron flow from MB in the presence of 1.4 mg/L sulfate. The data also suggest that when electron-donor availability was limited, SRB outcompeted MB for available substrate at a lower concentration of sulfate than when electron donor was plentiful. For example, in an area of limited electron-donor availability, SRB appeared to maintain dominance of electron flow at sulfate concentrations less than 1 mg/L. The presence of abundant electron donor and a limited amount of sulfate reduced competition for available substrate, allowing both SRB and MB to metabolize available substrates concurrently.

Environmental Science & Technology↗
USGS1996

Covalent binding of aniline to humic substances. 2. 15N NMR studies of nucleophilic addition reactions

Aromatic amines are known to undergo covalent binding with humic substances in the environment. Although previous studies have examined reaction conditions and proposed mechanisms, there has been no direct spectroscopic evidence for the covalent binding of the amines to the functional groups in humic substances. In order to further elucidate the reaction mechanisms, the Suwannee River and IHSS soil fulvic and humic acids were reacted with 15N-labeled aniline at pH 6 and analyzed using 15N NMR spectrometry. Aniline underwent nucleophilic addition reactions with the quinone and other carbonyl groups in the samples and became incorporated in the form of anilinohydroquinone, anilinoquinone, anilide, imine, and heterocyclic nitrogen, the latter comprising 50% or more of the bound amine. The anilide and anilinohydroquinone nitrogens were determined to be susceptible to chemical exchange by ammonia. In the case of Suwannee River fulvic acid, reaction under anoxic conditions and pretreatment with sodium borohydride or hydroxylamine prior to reaction under oxic conditions resulted in a decrease in the proportion of anilinohydroquinone nitrogen incorporated. The relative decrease in the incorporation of anilinohydroquinone nitrogen with respect to anilinoquinone nitrogen under anoxic conditions suggested that inter- or intramolecular redox reactions accompanied the nucleophilic addition reactions.

Environmental Science & Technology↗
USGS1996

Covalent binding of aniline to humic substances. 1. Kinetic studies

The reaction kinetics for the covalent binding of aniline with reconstituted IHSS humic and fulvic acids, unfractionated DOM isolated from Suwannee River water, and whole samples of Suwannee River water have been investigated. The reaction kinetics in each of these systems can be adequately described by a simple second-order rate expression. The effect of varying the initial concentration of aniline on reaction kinetics suggested that approximately 10% of the covalent binding sites associated with Suwannee River fulvic acid are highly reactive sites that are quickly saturated. Based on the kinetic parameters determined for the binding of aniline with the Suwannee River fulvic and humic acid isolates, it was estimated that 50% of the aniline concentration decrease in a Suwannee River water sample could be attributed to reaction with the fulvic and humic acid components of the whole water sample. Studies with Suwannee River fulvic acid demonstrated that the rate of binding decreased with decreasing pH, which parallels the decrease in the effective concentration of the neutral form, or reactive nucleophilic species of aniline. The covalent binding of aniline with Suwannee River fulvic acid was inhibited by prior treatment of the fulvic acid with hydrogen sulfide, sodium borohydride, or hydroxylamine. These observations are consistent with a reaction pathway involving nucleophilic addition of aniline to carbonyl moieties present in the fulvic acid.

Environmental Science & Technology↗
USGS1996

Comparison of denitrification activity measurements in groundwater using cores and natural-gradient tracer tests

The transport of many solutes in groundwater is dependent upon the relative rates of physical flow and microbial metabolism. Quantifying rates of microbial processes under subsurface conditions is difficult and is most commonly approximated using laboratory studies with aquifer materials. In this study, we measured in situ rates of denitrification in a nitrate-contaminated aquifer using small-scale, natural-gradient tracer tests and compared the results with rates obtained from laboratory incubations with aquifer core material. Activity was measured using the acetylene block technique. For the tracer tests, co-injection of acetylene and bromide into the aquifer produced a 30 μM increase in nitrous oxide after 10 m of transport (23−30 days). An advection−dispersion transport model was modified to include an acetylene-dependent nitrous oxide production term and used to simulate the tracer breakthrough curves. The model required a 4-day lag period and a relatively low sensitivity to acetylene to match the narrow nitrous oxide breakthrough curves. Estimates of in situ denitrification rates were 0.60 and 1.51 nmol of N 2 O produced cm - 3 aquifer day - 1 for two successive tests. Aquifer core material collected from the tracer test site and incubated as mixed slurries in flasks and as intact cores yielded rates that were 1.2−26 times higher than the tracer test rate estimates. Results with the coring-dependent techniques were variable and subject to the small-scale heterogeneity within the aquifer, while the tracer tests integrated the heterogeneity along a flow path, giving a rate estimate that is more applicable to transport at the scale of the aquifer.

Environmental Science & Technology↗
USGS1996

Anaerobic hydrocarbon degradation in petroleum-contaminated harbor sediments under sulfate-reducing and artificially imposed iron-reducing conditions

The potential use of iron(III) oxide to stimulate in-situ hydrocarbon degradation in anaerobic petroleum-contaminated harbor sediments was investigated. Previous studies have indicated that Fe(III)-reducing bacteria (FeRB) can oxidize some electron donors more effectively than sulfate- reducing bacteria (SRB). In contrast to previous results in freshwater sediments, the addition of Fe(III) to marine sediments from San Diego Bay, CA did not switch the terminal electron-accepting process (TEAP) from sulfate reduction to Fe-(III) reduction. Addition of Fe(III) also did not stimulate anaerobic hydrocarbon oxidation. Exposure of the sediment to air [to reoxidize Fe(II) to Fe(III)] followed by anaerobic incubation of the sediments, resulted in Fe-(III) reduction as the TEAP, but contaminant degradation was not stimulated and in some instances was inhibited. The difference in the ability of FeRB to compete with the SRB in the different sediment treatments was related to relative population sizes. Although the addition of Fe(III) did not stimulate hydrocarbon degradation, the results presented here as well as other recent studies demonstrate that there may be significant anaerobic hydrocarbon degradation under sulfate-reducing conditions in harbor sediments.

Environmental Science & Technology↗
USGS1996

Reactive solute transport in an acidic stream: Experimental pH increase and simulation of controls on pH, aluminum, and iron

Solute transport simulations quantitatively constrained hydrologic and geochemical hypotheses about field observations of a pH modification in an acid mine drainage stream. Carbonate chemistry, the formation of solid phases, and buffering interactions with the stream bed were important factors in explaining the behavior of pH, aluminum, and iron. The precipitation of microcrystalline gibbsite accounted for the behavior of aluminum; precipitation of Fe(OH)3 explained the general pattern of iron solubility. The dynamic experiment revealed limitations on assumptions that reactions were controlled only by equilibrium chemistry. Temporal variation in relative rates of photoreduction and oxidation influenced iron behavior. Kinetic limitations on ferrous iron oxidation and hydrous oxide precipitation and the effects of these limitations on field filtration were evident. Kinetic restraints also characterized interaction between the water column and the stream bed, including sorption and desorption of protons from iron oxides at the sediment-water interface and post-injection dissolution of the precipitated aluminum solid phase.

Environmental Science & Technology↗