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At least 343 records · Page 19Linked to original sources
USGS2000

Bioavailability of particle-associated Se to the bivalve Potamocorbula amurensis

Elemental selenium, Se(0), is a prevalent chemical form in sediments, but little is known about its bioavailability. We evaluated the bioavailability of two forms of Se(0) by generating radioisotopic 75 Se(0) through bacterial dissimilatory reduction of 75 SeO 3 2 - by pure bacterial cultures (SES) and by an anaerobic sediment microbial consortium (SED). A third form was generated by reducing 75 SeO 3 2 - with ascorbic acid (AA). Speciation determinations showed that AA and SES were >90% Se(0), but SED showed a mixture of Se(0), selenoanions, and a residual fraction. Pulse-chase techniques were used to measure assimilation efficiencies (AE) of these particulate Se forms by the bivalve Potamocorbula amurensis . Mean AE values were 3 ± 2% for AA, 7 ± 1% for SES, and 28 ± 15% for SED, showing that the bioavailability of reduced, particle-associated Se is dependent upon its origin. To determine if oxidative microbial processes increased Se transfer, SES 75 Se(0) was incubated with an aerobic sediment microbial consortium. After 113 d of incubation, 36% of SES Se(0) was oxidized to SeO 3 2 - . Assimilation of total particulate Se was unaffected however (mean AE = 5.5%). The mean AE from the diatom Phaeodactylum tricornutum was 58 ± 8%, verifying the importance of Se associated with biogenic particles. Speciation and AE results from SED suggest that selenoanion reduction in wetlands and estuaries produces biologically available reduced selenium.

Environmental Science & Technology↗
USGS2002

Accumulation by fish of contaminants released from dredged sediments

Inasmuch as the process of dredging and disposing of dredged materials causes a resuspension of these materials and an increase in bioavailability of associated contaminants, we conducted a series of experiments to examine the potential accumulation by fish of contaminants from suspended sediments. In the first experiment we compared accumulation of contaminants by yellow perch of hatchery and lake origin and found that after 10 days of exposure to nonaerated sediments, fish of hatchery origin accumulated PCBs and Fe, while fish of lake origin accumulated As, Cr, Fe, and Na. Two additional exposures were conducted to evaluate the effects of aerating the sediments prior to measuring bioavailability of associated contaminants. Fish of hatchery origin exposed to nonaerated sediments for 10 days accumulated PCBs and Hg, while fish of hatchery origin exposed to aerated sediments for 10 days accumulated PCBs, DDE, Zn, Fe, Cs, and Se. These results demonstrated not only the potential for uptake of contaminants by fish as a result of dredging but also the potential utility of fish bioassays in evaluating proposed dredging operations.

Environmental Science & Technology↗
USGS2000

Influence of acid volatile sulfide and metal concentrations on metal bioavailability to marine invertebrates in contaminated sediments

An 18-day microcosm study was conducted to evaluate the influence of acid volatile sulfides (AVS) and metal additions on bioaccumulation from sediments of Cd, Ni, and Zn in two clams ( Macoma balthica and Potamocorbula amurensis ) and three marine polychaetes ( Neanthes arenaceodentata, Heteromastus filiformis, and Spiophanes missionensis ). Manipulation of AVS by oxidation of naturally anoxic sediments allowed use of metal concentrations typical of nature and evaluation of processes important to chronic metal exposure. A vertical sediment column similar to that often found in nature was used to facilitate realistic biological behavior. Results showed that AVS or porewater (PW) metals controlled bioaccumulation in only 2 of 15 metal-animal combinations. Bioaccumulation of all three metals by the bivalves was related significantly to metal concentrations extracted from sediments (SEM) but not to [SEM − AVS] or PW metals. SEM predominantly influenced bioaccumulation of Ni and Zn in N. arenaceodentata , but Cd bioaccumulation followed PW Cd concentrations. SEM controlled tissue concentrations of all three metals in H. filiformis and S. missionensis , with minor influences from metal-sulfide chemistry. Significant bioaccumulation occurred when SEM was only a small fraction of AVS in several treatments. Three factors appeared to contribute to the differences between these bioaccumulation results and the results from toxicity tests reported previously: differences in experimental design, dietary uptake, and biological attributes of the species, including mode and depth of feeding.

Environmental Science & Technology↗
USGS2000

Influence of acid volatile sulfides and metal concentrations on metal partitioning in contaminated sediments

The influence of acid volatile sulfide (AVS) on the partitioning of Cd, Ni, and Zn in porewater (PW) and sediment as reactive metals (SEM, simultaneously extracted metals) was investigated in laboratory microcosms. Two spiking procedures were compared, and the effects of vertical geochemical gradients and infaunal activity were evaluated. Sediments were spiked with a Cd−Ni−Zn mixture (0.06, 3, 7.5 μmol/g, respectively) containing four levels of AVS (0.5, 7.5, 15, 35 μmol/g). The results were compared to sediments spiked with four levels of Cd−Ni−Zn mixtures at one AVS concentration (7.5 μmol/g). A vertical redox gradient was generated in each treatment by an 18-d incubation with an oxidized water column. [AVS] in the surface sediments decreased by 65−95% due to oxidation during incubation; initial [AVS] was maintained at 0.5−7.5 cm depth. PW metal concentrations were correlated with [SEM − AVS] among all data. But PW metal concentrations were variable, causing the distribution coefficient, Kd pw (the ratio of [SEM] to PW metal concentrations) to vary by 2−3 orders of magnitude at a given [SEM − AVS]. One reason for the variability was that vertical profiles in PW metal concentrations appeared to be influenced by diffusion as well as [SEM − AVS]. The presence of animals appeared to enhance the diffusion of at least Zn. The generalization that PW metal concentrations are controlled by [SEM − AVS] is subject to some important qualifications if vertical gradients are complicated, metal concentrations vary, or equilibration times differ.

Environmental Science & Technology↗
USGS2000

Mobilization of arsenite by dissimilatory reduction of adsorbed arsenate

Sulfurospirillum barnesii is capable of anaerobic growth using ferric iron or arsenate as electron acceptors. Cell suspensions of S. barnesii were able to reduce arsenate to arsenite when the former oxyanion was dissolved in solution, or when it was adsorbed onto the surface of ferrihydrite, a common soil mineral, by a variety of mechanisms (e.g., coprecipitation, presorption). Reduction of Fe(III) in ferrihydrite to soluble Fe(II) also occurred, but dissolution of ferrihydrite was not required in order for adsorbed arsenate reduction to be achieved. This was illustrated by bacterial reduction of arsenate coprecipitated with aluminum hydroxide, a mineral that does not undergo reductive dissolution. The rate of arsenate reduction was influenced by the method in which arsenate became associated with the mineral phases and may have been strongly coupled with arsenate desorption rates. The extent of release of arsenite into solution was governed by adsorption of arsenite onto the ferrihydrite or alumina phases. The results of these experiments have interpretive significance to the mobilization of arsenic in large alluvial aquifers, such as those of the Ganges in India and Bangladesh, and in the hyporheic zones of contaminated streams.Sulfurospirillum barnesii is capable of anaerobic growth using ferric iron or arsenate as electron acceptors. Cell suspensions of S. barnesii were able to reduce arsenate to arsenite when the former oxyanion was dissolved in solution, or when it was adsorbed onto the surface of ferrihydrite a common soil mineral, by a variety of mechanisms (e.g., coprecipitation, presorption). Reduction of Fe(III) in ferrihydrite to soluble Fe(II) also occurred, but dissolution of ferrihydrite was not required in order for adsorbed arsenate reduction to be achieved. This was illustrated by bacterial reduction of arsenate coprecipitated with aluminum hydroxide, a mineral that does not undergo reductive dissolution. The rate of arsenate reduction was influenced by the method in which arsenate became associated with the mineral phases and may have been strongly coupled with arsenate desorption rates. The extent of release of arsenite into solution was governed by adsorption of arsenite onto the ferrihydrite or alumina phases. The results of these experiments have interpretive significance to the mobilization of arsenic in large alluvial aquifers, such as those of the Ganges in India and Bangladesh, and in the hyporheic zones of contaminated streams.

Environmental Science & Technology↗
USGS2000

Comparing polychlorinated biphenyl concentrations and patterns in the Saginaw River using sediment, caged fish, and semipermeable membrane devices

Three techniques of assessing bioavailable polychlorinated biphenyls (PCBs) in the Saginaw River, MI, were compared: sediments, caged fish, and semipermeable membrane devices (SPMDs). SPMDs and caged fish were placed in the river for 28 days at five sites where sediments were also sampled. The samples were analyzed for PCB congeners to determine concentrations and patterns. Total PCB concentrations ranged from 33 to 280 ng/g (dry weight) in sediments, 46 to 290 ng/g (wet weight) in caged fish, and 77 to 790 ng/g in SPMDs. Previously reported rates of PCB accumulation by SPMDs were used to estimate aqueous concentrations from the PCB concentrations detected in the SPMDs. Sediment-water partition coefficients were used to estimate aqueous PCB concentrations from sediment. Steady-state bioconcentration factors and depuration rate constants were used to estimate dissolved PCB concentrations from caged channel catfish. Relative PCB patterns from the SPMDs, caged fish, and sediment were compared using principal components analysis. SPMD and sediment samples provide complementary information. Sediments reflect long-term accumulation and weathering, while SPMDs integrate water concentrations only during the sampling period. Because of higher water solubilities of lower-chlorinated PCBs these predominate in the SPMDs as compared to in the fish and sediments. Contaminant profile differences between caged fish and SPMDs are likely due to metabolism and depuration of certain PCB congeners by fish.Three techniques of assessing bioavailable polychlorinated biphenyls (PCBs) in the Saginaw River, Ml, were compared: sediments, caged fish, and semipermeable membrane devices (SPMDs). SPMDs and caged fish were placed in the river for 28 days at five sites where sediments were also sampled. The samples were analyzed for PCB congeners to determine concentrations and patterns. Total PCB concentrations ranged from 33 to 280 ng/g (dry weight) in sediments, 46 to 290 ng/g (wet weight) in caged fish, and 77 to 790 ng/g in SPMDs. Previously reported rates of PCB accumulation by SPMDs were used to estimate aqueous concentrations from the PCB concentrations detected in the SPMDs. Sediment-water partition coefficients were used to estimate aqueous PCB concentrations from sediment. Steady-state bioconcentration factors and depuration rate constants were used to estimate dissolved PCB concentrations from caged channel catfish. Relative PCB patterns from the SPMDs, caged fish, and sediment were compared using principal components analysis. SPMD and sediment samples provide complementary information. Sediments reflect long-term accumulation and weathering, while SPMDs integrate water concentrations only during the sampling period. Because of higher water solubilities of lower-chlorinated PCBs these predominate in the SPMDs as compared to in the fish and sediments. Contaminant profile differences between caged fish and SPMDs are likely due to metabolism and depuration of certain PCB congeners by fish.At five sites in the Saginaw River, MI, PCB concentrations were determined in the summer of 1993 using three methods: sediment analysis, concentrations in caged fish, and concentrations in semipermeable membrane devices (SPMDs). On average, total PCB concentrations in the SPMDs were twice those found in caged fish, and the SPMD-to-fish concentration ratios of di-, tri-, tetra-, and pentaCB homologues were 10.0, 3.0, 2.5, and 1.4, respectively. Average concentrations in the sediments were approximately half those in the SPMDs, and the caged fish showed a greater preponderance of higher log octanol-water partition coefficient PCBs similar to the sediment pattern. On average, the water PCB concentrations estimated from sediment concentrations were five times higher than those calculated from SPMDs and three times higher than those estimated from caged fish. The total PCB concentrations in sediment, caged fish, and SPMDs ranged 33-280, 46-290, and 77-790 ng/g, respectiv

Environmental Science & Technology↗
USGS2001

Effect of scale on the behavior of atrazine in surface waters

Field runoff is an important transport mechanism by which agricultural pesticides, including atrazine, move into the hydrologic environment. Atrazine is chosen because it is widely used, is transported in runoff relatively easily, is widely observed in surface waters, and has relatively little loss in the stream network. Data on runoff of atrazine from experimental plot and field studies is combined with annual estimates of load in numerous streams and rivers, resulting in a data set with 408 observations that span 14 orders of magnitude in area. The load as a percent of use (LAPU) on an annual basis is the parameter that is compared among the studies. There is no difference in the mean or range of LAPU values for areas from the size of experimental field plots (???0.000023 ha) and small watersheds (<100 000 ha). The relatively invariant LAPU value observed across a large range of watershed areas implies that the characteristics of atrazine itself (application method and chemical properties) are important in determining the extent of runoff. The variable influences on the extent of runoff from individual watershed characteristics and weather events are superimposed on the relatively invariant LAPU value observed across the range of watershed areas. The results from this study establish the direct relevance for agricultural field plot studies to watershed studies across the full range of scale.

Environmental Science & Technology↗
USGS2000

Cytochrome P450 1A expression in midwater fishes: Potential effects of chemical contaminants in remote oceanic zones

Cytochrome P450 1A (CYP1A) induction is a robust marker for exposure to polynuclear aromatic hydrocarbons and planar halogenated aromatic hydrocarbons that are aryl hydrocarbon receptor agonists. We examined CYP1A expression in mesopelagic fishes from the western North Atlantic. Individuals in 22 species were obtained from slope water and the Sargasso Sea in 1977, 1978, and 1993. Aryl hydrocarbon hydroxylase (AHH), a CYP1A activity, was detected in liver from all species in 1977/78. In some, including Gonostoma elongatum, AHH was inhibited by the CYP1A inhibitor ??-naphthoflavone. CYP1A-dependent ethoxyresorufin O-deethylase (EROD) was detected in liver microsomes of all species in 1993; rates were highest in G. elongatum and Argyropelecus aculeatus. Immunoblot analysis with the CYP1A-specific monoclonal antibody 1-12-3 detected a single microsomal protein band in most 1993 samples; the highest content was in G. elongatum. Immunohistochemical analysis showed CYP1A staining in gill, heart, kidney, and/or liver of several species. Extracts of the 1993 G. elongatum and A. aculeatus, when applied to fish hepatoma cells (PLHC-1) in culture, elicited a significant induction of EROD in those cells. The capacity of the extracts to induce CYP1A correlated with the content of PCBs measured in the same fish (2-4.6 ng/g total body weight). Mesopelagic fish in the western North Atlantic, which experience no direct exposure to surface waters or sediments, are exposed chronically to inducers of CYP1A at levels that appear to be biochemically active in those fish.Cytochrome P450 1A (CYP1A) induction is a robust marker for exposure to polynuclear aromatic hydrocarbons and planar halogenated aromatic hydrocarbons that are awl hydrocarbon receptor agonists. We examined CYP1A expression in mesopelagic fishes from the western North Atlantic. Individuals in 22 species were obtained from slope water and the Sargasso Sea in 1977, 1978, and 1993. Aryl hydrocarbon hydroxylase (AHH), a CYP1A activity, was detected in liver from all species in 1977/78. In some, including Gonostoma elongatum, AHH was inhibited by the CYP1A inhibitor ??-naphthoflavone. CYP1A-dependent ethoxyresorufin O-deethylase (EROD) was detected in liver microsomes of all species in 1993; rates were highest in G. elongatum and Argyropelecus aculeatus. Immunoblot analysis with the CYP1A-specific monoclonal antibody 1-12-3 detected a single microsomal protein band in most 1993 samples; the highest content was in G. elongatum. Immunohistochemical analysis showed CYP1A staining in gill, heart, kidney, and/or liver of several species. Extracts of the 1993 G. elongatum and A. aculeatus, when applied to fish hepatoma cells (PLHC-1) in culture, elicited a significant induction of EROD in those cells. The capacity of the extracts to induce CYP1A correlated with the content of PCBs measured in the same fish (2-4.6 ng/g total body weight). Mesopelagic fish in the western North Atlantic, which experience no direct exposure to surface waters or sediments, are exposed chronically to inducers of CYP1A at levels that appear to be biochemically active in those fish.

Environmental Science & Technology↗
USGS2000

Occurrence of nitrous oxide in the central High Plains aquifer, 1999

Nitrogen-enriched groundwater has been proposed as an important anthropogenic source of atmospheric nitrous oxide (N2O), yet few measurements of N2O in large aquifer systems have been made. Concentrations of N2O in water samples collected from the 124 000 km2 central High Plains aquifer in 1999 ranged from < 1 to 940 nM, with a median concentration of 29 nM (n = 123). Eighty percent of the N20 concentrations exceeded the aqueous concentration expected from equilibration with atmospheric N2O. Measurements of N2O, NO3-, and 3H in unsaturated-zone sediments, recently recharged groundwater, and older groundwater indicate that concentrations of N2O in groundwater increased over time and will likely continue to increase in the future as N-enriched water recharges the aquifer. Large concentrations of O2 and NO3- and small concentrations of NH4+ and dissolved organic carbon in the aquifer indicate that N2O in the central High Plains aquifer was produced primarily by nitrification. Calculations indicate that the flux of N2O from the central High Plains aquifer to the atmosphere from well pumping and groundwater discharge to streams was not a significant source of atmospheric N2O.Nitrogen-enriched groundwater has been proposed as an important anthropogenic source of atmospheric nitrous oxide (N2O), yet few measurements of N2O in large aquifer systems have been made. Concentrations of N2O in water samples collected from the 124000 km2 central High Plains aquifer in 1999 ranged from < 1 to 940 nM, with a median concentration of 29 nM (n = 123). Eighty percent of the N2O concentrations exceeded the aqueous concentration expected from equilibration with atmospheric N2O. Measurements of N2O, NO3-, and 3H in unsaturated-zone sediments, recently recharged groundwater, and older groundwater indicate that concentrations of N2O in groundwater increased over time and will likely continue to increase in the future as N-enriched water recharges the aquifer. Large concentrations of O2 and NO3- and small concentrations of NH4+ and dissolved organic carbon in the aquifer indicate that N2O in the central High Plains aquifer was produced primarily by nitrification. Calculations indicate that the flux of N2O from the central High Plains aquifer to the atmosphere from well pumping and groundwater discharge to streams was not a significant source of atmospheric N2O.Water samples were collected from 92 domestic wells, 16 monitoring wells and 15 public-supply wells in the High Plains Aquifer in 1999, and concentrations of nitrous oxide were measured. The groundwater concentrations ranged from less than 1 to 940 nM. Concentrations expressed as a percent of saturation in water ranged from less than 10 to 9690%. A significant decrease was noted in N2O concentrations with increasing depth of the well screen below the water table, and a significant positive correlation was found between the concentrations of N2O and nitrate. The small area-averaged N2O emission rate for the aquifer indicated that it was not an important component of the atmospheric N2O budget, but the importance could increase as groundwater N2O concentrations increase.

Environmental Science & Technology↗
USGS2000

Enantiomeric composition of chiral polychlorinated biphenyl atropisomers in aquatic bed sediment

Enantiomeric ratios (ERs) for eight polychlorinated biphenyl (PCB) atropisomers were measured in aquatic sediment from selected sites throughout the United States by using chiral gas chromatography/mass spectrometry. Nonracemic ERs for PCBs 91, 95, 132, 136, 149, 174, and 176 were found in sediment cores from Lake Hartwell, SC, which confirmed previous inconclusive reports of reductive dechlorination of PCBs at these sites on the basis of achiral measurements. Nonracemic ERs for many of the atropisomers were also found in bed-sediment samples from the Hudson and Housatonic Rivers, thus indicating that some of the PCB biotransformation processes identified at these sites are enantioselective. Patterns in ERs among congeners were consistent with known reductive dechlorination patterns at both river sediment basins. The enantioselectivity of PCB 91 is reversed between the Hudson and Housatonic River sites, which implies that the two sites have different PCB biotransformation processes with different enantiomer preferences.Enantiomeric ratios (ERs) for eight polychlorinated biphenyl (PCB) atropisomers were measured in aquatic sediment from selected sites throughout the United States by using chiral gas chromatography/mass spectrometry. Nonracemic ERs for PCBs 91, 95, 132, 136, 149, 174, and 176 were found in sediment cores from Lake Hartwell, SC, which confirmed previous inconclusive reports of reductive dechlorination of PCBs at these sites on the basis of achiral measurements. Nonracemic ERs for many of the atropisomers were also found in bed-sediment samples from the Hudson and Housatonic Rivers, thus indicating that some of the PCB biotransformation processes identified at these sites are enantioselective. Patterns in ERs among congeners were consistent with known reductive dechlorination patterns at both river sediment basins. The enantioselectivity of PCB 91 is reversed between the Hudson and Housatonic River sites, which implies that the two sites have different PCB biotransformation processes with different enantiomer preferences.

Environmental Science & Technology↗
USGS2002

Effect of censoring trace-level water-quality data on trend-detection capability

Monte Carlo experiments were used to evaluate whether trace-level water-quality data that are routinely censored (not reported) contain valuable information for trend detection. Measurements are commonly censored if they fall below a level associated with some minimum acceptable level of reliability (detection limit). Trace-level organic data were simulated with best- and worst-case estimates of measurement uncertainty, various concentrations and degrees of linear trend, and different censoring rules. The resulting classes of data were subjected to a nonparametric statistical test for trend. For all classes of data evaluated, trends were most effectively detected in uncensored data as compared to censored data even when the data censored were highly unreliable. Thus, censoring data at any concentration level may eliminate valuable information. Whether or not valuable information for trend analysis is, in fact, eliminated by censoring of actual rather than simulated data depends on whether the analytical process is in statistical control and bias is predictable for a particular type of chemical analyses.

Environmental Science & Technology↗
USGS2000

Fate and origin of 1,2-dichloropropane in an unconfined shallow aquifer

A shallow aquifer with different redox zones overlain by intensive agricultural activity was monitored for the occurrence of 1,2-dichloropropane (DCP) to assess the fate and origin of this pollutant. DCP was detected more frequently in groundwater samples collected in aerobic and nitrate-reducing zones than those collected from iron-reducing zones. Simulated DCP concentrations for groundwater entering an iron-reducing zone were calculated from a fate and transport model that included dispersion, sorption, and hydrolysis but not degradation. Simulated concentrations were well in excess of measured values, suggesting that microbial degradation occurred in the iron-reducing zone. Microcosm experiments were conducted using aquifer samples collected from iron-reducing and aerobic zones to evaluate the potential for microbial degradation of DCP and to explain field observations. Hydrogenolysis of DCP and production of monochlorinated propanes in microcosm experiments occurred only with aquifer materials collected from the iron-reducing zone, and no dechlorination was observed in microcosms established with aquifer materials collected from the aerobic zones. Careful analyses of the DCP/1,2,2-trichloropropane ratios in groundwater indicated that older fumigant formulations were responsible for the high levels of DCP present in this aquifer.A shallow aquifer with different redox zones overlain by intensive agricultural activity was monitored for the occurrence of 1,2-dichloropropane (DCP) to assess the fate and origin of this pollutant. DCP was detected more frequently in groundwater samples collected in aerobic and nitrate-reducing zones than those collected from iron-reducing zones. Simulated DCP concentrations for groundwater entering an iron-reducing zone were calculated from a fate and transport model that included dispersion, sorption, and hydrolysis but not degradation. Simulated concentrations were well in excess of measured values, suggesting that microbial degradation occurred in the iron-reducing zone. Microcosm experiments were conducted using aquifer samples collected from iron-reducing and aerobic zones to evaluate the potential for microbial degradation of DCP and to explain field observations. Hydrogenolysis of DCP and production of monochlorinated propanes in microcosm experiments occurred only with aquifer materials collected from the iron-reducing zone, and no dechlorination was observed in microcosms established with aquifer materials collected from the aerobic zones. Careful analyses of the DCP/1,2,2-trichloropropane ratios in groundwater indicated that older fumigant formulations were responsible for the high levels of DCP present in this aquifer.

Washington↗