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Evaluation of lipid-containing semipermeable membrane devices for monitoring organochlorine contaminants in the Upper Mississippi river

Organochlorine contaminants sequestered in lipid-containing semipermeable membrane devices (SPMDs) were compared to those found in tangential-flow ultrafilter permeates as part of a pilot study at 10 sites in the Upper Mississippi River system. Caged and feral fish from three primary sites were also analyzed for comparison. Concentrated organochlorine (OC) compounds were readily extracted from the SPMDs by dialysis into hexane, and samples were analyzed by gas chromatography-negative chemical ionization-mass spectrometry. Fish and water samples were processed by conventional methods. Reasonable agreement was found between analyte SPMD-derived water concentrations and measured values of ultrafilter permeates; however, concentrations of the same analytes in caged fish did not appear to be proportional to water concentrations derived from SPMDs and ultrafilter permeates. The greatest number of OC compounds was detected in SPMDs; fewer were detected in caged fish and feral fish.

Illinois, Iowa, Minnesota, Missouri, Wisconsin↗

Toxicity and bioaccumulation of sediment-associated contaminants using freshwater invertebrates: A review of methods and applications

This paper reviews recent developments in methods for evaluating the toxicity and bioaccumulation of contaminants associated with freshwater sediments and summarizes example case studies demonstrating the application of these methods. Over the past decade, research has emphasized development of more specific testing procedures for conducting 10-d toxicity tests with the amphipod Hyalella azteca and the midge Chironomus tentans. Toxicity endpoints measured in these tests are survival for H. azteca and survival and growth for C. tentans. Guidance has also been developed for conducting 28-d bioaccumulation tests with the oligochaete Lumbriculus variegatus, including determination of bioaccumulation kinetics for different compound classes. These methods have been applied to a variety of sediments to address issues ranging from site assessments to bioavailability of organic and inorganic contaminants using field-collected and laboratory-spiked samples. Survival and growth of controls routinely meet or exceed test acceptability criteria. Results of laboratory bioaccumulation studies with L. variegatus have been confirmed with comparisons to residues (PCBs, PAHs, DDT) present from synoptically collected field populations of oligochaetes. Additional method development is currently underway to develop chronic toxicity tests and to provide additional data-confirming responses observed in laboratory sediment tests with natural benthic populations.

Environmental Toxicology and Chemistry↗

Acephate affects migratory orientation of the white-throated sparrow (Zonotrichia albicollis)

Migratory white-throated sparrows ( Zonotrichia albicollis ) were exposed to acephate (acetylphosphoramidothioic acid O, S -dimethyl ester), an organophosphorus pesticide, to determine its effects on migratory orientation and behavior. Birds were also exposed to polarizer sheets to determine the mechanism by which acephate may affect migratory orientation. Adult birds exposed to 256 ppm acephate a.i. were not able to establish a preferred migratory orientation and exhibited random activity. All juvenile treatment groups displayed a seasonally correct southward migratory orientation. We hypothesize that acephate may have produced aberrant migratory behavior by affecting the memory of the migratory route and wintering ground. This experiment reveals that an environmentally relevant concentration of a common organophosphorus pesticide can alter migratory orientation, but its effect is markedly different between adult and juvenile sparrows. Results suggest that the survival of free-flying adult passerine migrants may be compromised following organophosphorus pesticide exposure.

Environmental Toxicology and Chemistry↗

Temporal and vertical distribution of total ammonia nitrogen and un-ionized ammonia nitrogen in sediment pore water from the upper Mississippi River

We examined the temporal and vertical distribution of total ammonia nitrogen (TAN) and un-ionized ammonia nitrogen (NH 3 -N) in sediment pore water and compared the temporal patterns of TAN and NH 3 -N concentrations in overlying surface water with those in pore water. Pore water was obtained by core extraction and subsequent centrifugation. We measured TAN concentrations and calculated NH 3 -N concentrations from February through October 1993 at four sites in Pool 8, upper Mississippi River, at depths of 0 to 4, 4 to 8, and 8 to 12 cm below the sediment-water interface. Total ammonia nitrogen and NH 3 -N concentrations were significantly different among sampling dates ( p = 0.0001) and sediment depths ( p = 0.0001). Concentrations of TAN and NH 3 -N in surface water were significantly less than those in pore water from all sediment depths ( p < 0.05). Concentrations in pore water ranged from 0.07 to 4.0 mg TAN/L and less than 1 to 20 μg NH 3 -N/L in winter, and from 0.07 to 10.0 mg TAN/L and 1 to 175 μg NH 3 -N/L in summer; greatest concentrations were usually found in sediments 8 to 12 cm deep. Annual mean TAN concentrations were positively correlated with silt and volatile solids content and were negatively correlated with sand content. Because of the high variability of TAN and NH 3 -N concentrations in pore water, sediment toxicity studies should take into account the season and the depth at which sediments are obtained. The annual mean NH 3 -N concentration in pore water at one site (55 μg/L) exceeded the concentration (30 μg/L) demonstrated to inhibit growth of fingernail clams in laboratory studies. However, these concentrations apparently were not lethal, as evidenced by the presence of fingernail clams at this site.

Environmental Toxicology and Chemistry↗

Quality control considerations for the determination of acid-volatile sulfide and simultaneously extracted metals in sediments

The determination of acid-volatile sulfide (AVS) and simultaneously extracted metals (SEMs) in sediment by treatment with dilute HCl shows promise as a tool for predicting the potential for metal toxicity to sediment-dwelling organisms. Effective quality control measures must be developed if this method is to become a reliable procedure and to ensure comparability of data. However, establishing quality control measures that assess procedural errors for an operationally defined method can be problematic. For example, preextraction spikes added for assessing the accuracy of AVS and SEMs may be poorly recovered due to adsorption or reaction with sediment constituents. For a variety of sediment types, we found preextraction spikes of sulfide, mercury, and copper to be prone to variable recoveries for the AVS/SEM procedure; recoveries averaged 76.3% (SD, 20.9) for sulfide, 61.9% (39.6) for Hg, and 90.1% (12.7) for Cu. The average recovery was near 100% for preextraction spikes of sediments for Cd, Ni, Pb, and Zn, and the recoveries of preextraction blank spikes for all analytes were consistently 95 to 105%. Binding of Cu or Hg with sulfides is sufficiently strong that 1 N hydrochloric acid will not necessarily keep the spiked metal in the dissolved state. This does not mean that the SEM procedure is invalid for these metals, only that the quality control of procedural error is difficult to assess. However, Hg will generally not be detected when measured as an SEM because of its tendency to adsorb onto sulfide minerals even at extremely low pH. Some reference sediments may be useful for assessing consistency of AVS determinations; we measured 5.97 ± 0.65 μmol/g in National Institute of Standards and Technology (NIST) 1645 and 1.34 ± 0.14 μmol/g in NIST 2704 for repeated determinations conducted over the past 3 years. Apparently, some sediments may contain an oxidation-resistant sulfide component that can release low to moderate AVS when treated with dilute HCl.

Environmental Toxicology and Chemistry↗

Effects of spatial and temporal variation of acid-volatile sulfide on the bioavailability of copper and zinc in freshwater sediments

Variation in concentrations of acid-volatile sulfide (AVS) in sediments from the upper Clark Fork River of Montana, USA, was associated with differences in bioaccumulation of Cu and Zn and growth of larvae of the midge, Chironomus tentans . Growth of midge larvae was significantly greater and bioaccumulation of Cu was significantly less in surface sections (0–3 cm depth) of sediment cores, which had greater concentrations of AVS and lesser ratios of simultaneously extracted metals to AVS (SEM:AVS ratios) than in subsurface sediments (6–9 cm). Concentrations of AVS were significantly less in sediments incubated with oxic overlying water for 9 weeks than in the same sediments incubated under anoxic conditions. Bioaccumulation of Cu differed significantly between incubation treatments, corresponding to differences in concentrations of AVS and SEM:AVS ratios, although midge growth did not. Bioaccumulation of Zn did not differ significantly between depth strata of sediment cores or between incubation treatments. When results from the two sets of bioassays were combined, bioaccumulation of Cu and Zn, but not growth, was significantly correlated with SEM:AVS ratios and other estimates of bioavailable metal fractions in sediments. Growth of midge larvae was significantly correlated with bioaccumulation of Zn, but not Cu, suggesting that Zn was the greater contributor to the toxicity of these sediments. Assessments of the toxicity of metal-contaminated freshwater sediments should consider the effects of spatial and temporal variation in AVS concentrations on metal bioavailability.

Environmental Toxicology and Chemistry↗

Monitoring exposure of nestling songbirds to agricultural application of an organophosphorus insecticide using cholinesterase activity

In June 1992 we collected 53 blood plasma samples from nestling red‐winged blackbirds ( Agelaius phoeniceus ), house sparrows ( Passer domesticus ), and brown‐headed cowbirds ( Molothrus ater ) at five study sites in northwestern Minnesota to evaluate the feasibility of using plasma and brain cholinesterase (ChE) activity and reactivation as a means of assessing exposure of nontarget organisms to the operational use of ChE‐ inhibiting insecticides in an agricultural setting. Three sites were adjacent to sugar beet fields that were likely to be treated with chlorpyrifos as Lorsban® (an organophosphorus [OP] insecticide) for control of sugar beet root maggot ( Tetanops myopaeformis ), and two sites were distant from fields likely to be treated (reference sites). Application of chlorpyrifos in fields surrounding study plots was monitored through contact with landowners and direct observations. Cholinesterase activity levels (total cholinesterase [ChE], acetylcholinesterase [AChE], and butyrylcholinesterase [BChE]) in nestling plasma were measured and tested for reactivation (ChE and AChE) in the presence of 2–PAM, an indication of exposure to an organophosphorus insecticide. In addition, 11 nestlings were euthanatized and in these samples we measured brain ChE activity and reactivation, and we analyzed gastrointestinal tracts and carcass washes for chlorpyrifos residues. Total ChE and BChE activity were lowest in similar‐aged nestlings at sites adjacent to treated beet fields (ChE, t = −2.51, d.f. = 21, p = 0.033; BChE, t = −2.56, d.f. = 21, p = 0.043). Nestlings from sites that were near fields where chlorpyrifos was applied were more likely to exhibit plasma AChE reactivation than nestlings from reference sites where OP or carbamate insecticide application was improbable (x 2 = 3.805, d.f. = 1, p ∼ 0.05). The magnitude of plasma ChE reactivation was highest within 1 to 3 d of insecticide application, although significant reactivation was measured up to 11 d after application of chlorpyrifos. Plasma AChE reactivation in the presence of pyridine‐2–aldoxime methochloride (2–PAM) appeared to be a more sensitive indicator of exposure to chlorpyrifos than plasma ChE or BChE activity levels.

Environmental Toxicology and Chemistry↗

Reproductive success, developmental anomalies and environmental contaminants in double-crested cormorants (Phalacrocorax auritus)

To test an association between environmental contaminants and the prevalence of congenital anomalies in colonial waterbirds, we collected representative eggs for chemical analysis from double-crested cormorant nests at colonies in Lake Michigan, Wisconsin, USA, and Lake Winnipegosis, Manitoba, Canada, and periodically revisited the nests to determine the hatching success, survivorship of hatchlings, and number of deformed hatchlings in the remainder of each clutch. Total concentrations of polychlorinated biphenyls (PCBs) in eggs were determined by capillary gas chromatography. The combined activity of planar chlorinated hydrocarbons (PCHs) in the eggs was measured in an in vitro bioassay based on the induction of ethoxyresorufin- O -deethylase (EROD) activity in rat hepatoma cells. The combined EROD induction activity was expressed as 2,3,7,8–tetrachlorodibenzo- p -dioxin equivalents (TCDD-EQ). Total concentrations of PCBs and TCDD-EQ were seven to eight times greater in eggs from Lake Michigan (7.8 μg/g and 138 pg/g, respectively) than in those from Lake Winnipegosis (1.0 μg/g and 19 pg/g, respectively). The proportion of eggs hatching at the Lake Michigan colony (59%) was less ( p < 0.05) than at Lake Winnipegosis (70%), and the prevalence of hatchlings with deformed bills was greater ( p < 0.001) at Lake Michigan (0.79 vs. 0.06%). However, within the Lake Michigan colony, concentrations of PCBs and TCDD-EQ were not correlated with either hatching success or the occurrence of deformities in nestlings.

Manitoba, Wisconsin↗

Cytochrome P450 and contaminant concentrations in nestling black-crowned night-herons and their interrelation with sibling embryos

Hepatic cytochrome P450-associated monooxygenase activities were measured in 11-d-old nestling black-crowned night-herons ( Nycticorax nycticorax ) collected from a reference site (next to Chincoteague National Wildlife Refuge, VA, USA) and three contaminated sites (Cat Island, Green Bay, WI, USA; Bair Island, San Francisco Bay, CA, USA; and West Marin Island, San Francisco Bay, CA, USA). Arylhydrocarbon hydroxylase and benzyloxyresorufin- O -dealkylase activities of nestlings from contaminated sites were only slightly elevated (less than threefold) compared with the reference site. Organochlorine pesticide and total polychlorinated biphenyl (PCB) concentrations in nestlings were greatest at contaminated sites, although much lower than found in concurrently collected eggs and pipping embryos. Pollutant concentrations of nestlings were rarely associated with monooxygenase activity. In contrast, concurrently collected pipping heron embryos (often siblings of the nestlings) exhibited pronounced monooxygenase induction (means at contaminated sites were elevated up to sevenfold and values of some embryos exceeded 25-fold induction). Furthermore, monooxygenase activity of pipping embryos was significantly correlated with total PCBs, arylhydrocarbon receptor-active PCB congeners, and toxic equivalents. The modest monooxygenase responses of heron nestlings suggest that this biomarker may have only limited value during this rapid-growth life stage.

California, Virginia, Wisconsin↗

Congener-specific polychlorinated biphenyl patterns in eggs of aquatic birds from the lower Laguna Madre, Texas

Eggs from four aquatic bird species nesting in the Lower Laguna Madre, Texas, were collected to determine differences and similarities in the accumulation of congener-specific polychlorinated biphenyls (PCBs) and to evaluate PCB impacts on reproduction. Because of the different toxicities of PCB congeners, it is important to know which congeners contribute most to total PCBs. The predominant PCB congeners were 153, 138, 180, 110, 118, 187, and 92. Collectively, congeners 153, 138, and 180 accounted for 26 to 42% of total PCBs. Congener 153 was the most abundant in Caspian terns (Sterna caspia) and great blue herons (Ardea herodias) and congener 138 was the most abundant in snowy egrets (Egretta thula) and tricolored herons (Egretta tricolor) . Principal component analysis indicated a predominance of higher chlorinated biphenyls in Caspian terns and great blue herons and lower chlorinated biphenyls in tricolored herons. Snowy egrets had a predominance of pentachlorobiphenyls. These results suggest that there are differences in PCB congener patterns in closely related species and that these differences are more likely associated with the species' diet rather than metabolism. Total PCBs were significantly greater ( p < 0.05) in Caspian terns than in the other species. Overall, PCBs in eggs of birds from the Lower Laguna Madre were below concentrations known to affect bird reproduction.

Environmental Toxicology and Chemistry↗

Effects of boron and selenium on mallard reproduction and duckling growth and survival

Boron (B) and selenium (Se) sometimes occur together in high concentrations in the environment and can accumulate in plants and invertebrates consumed by waterfowl. One hundred twenty-six pairs of breeding mallards (Anas platyrhynchos) were fed diets supplemented with B (as boric acid) at 0, 450, or 900 ppm, in combination with Se (as seleno-DL-methionine) at 0, 3.5, or 7 ppm, in a replicated factorial experiment. Ducklings produced received the same treatment combination as their parents. Boron and Se accumulated in adult liver, egg, and duckling liver. In adults, B and Se caused weight loss, and B decreased hemoglobin concentration, egg weight, and egg fertility. Both B and Se reduced hatching success and duckling weight, and B reduced duckling growth and duckling production, and caused several alterations in duckling liver biochemistry. Duckling survival was not reduced by B or Se, and neither B nor Se had histopathologic effects on adult or duckling liver, kidney, or spleen. There was little evidence of interaction between B and Se. This study demonstrated that B and Se, in the chemical forms and at the dietary levels administered in this study, can adversely affect mallard reproduction and duckling growth.

Environmental Toxicology and Chemistry↗

Sediment quality assessment studies of Tampa bay, Florida

A survey of the toxicity of sediments throughout the Tampa Bay estuary was performed as part of the National Oceanic and Atmospheric Administration's National Status and Trends Program. The objectives of the survey were to determine the spatial extent and severity of toxicity and to identify relationships between chemical contamination and toxicity. Three independent toxicity tests were performed: a 10-d amphipod survival test of the whole sediments with Ampelisca abdita , a sea urchin fertilization test of sediment pore water with Arbacia punctulata , and a 5-min Microtox® bioluminescence test with solvent extracts of the sediments. Seventy-three percent of the 165 undiluted sediment pore-water samples were significantly toxic relative to reference samples with the sea urchin fertilization test. In contrast, only 2% of the 165 samples were significantly toxic in the amphipod tests. The causes of toxicity were not determined. However, concentrations of numerous trace metals, pesticides, polychlorinated biphenyl (PCB) congeners, polycyclic aromatic hydrocarbons (PAHs), and ammonia were highly correlated with pore-water toxicity. Concentrations of many substances, especially total dichlorodiphenyltrichloroethanes (DDTs), endrin, total PCBs, certain PAHs, lead, and zinc, occurred at concentrations in the toxic samples that equaled or exceeded concentrations that have been previously associated with sediment toxicity.

Florida↗

Interlaboratory study of precision: Hyalella azteca and Chironomus tentans freshwater sediment toxicity assays

Standard 10-d whole-sediment toxicity test methods have recently been developed by the U.S. Environmental Protection Agency (EPA) for the amphipod Hyalella azteca and the midge Chironomus tentans . An interlaboratory evaluation of method precision was performed using a group of seven to 10 laboratories, representing government, academia, and environmental consulting firms. The test methods followed the EPA protocols for 4-d water-only reference toxicant (KCl) testing (static exposure) and for 10-d whole-sediment testing. Test sediments included control sediment, two copper-containing sediments, and a sediment contaminated primarily with polycyclic aromatic hydrocarbons. Reference toxicant tests resulted in H. azteca and C. tentans median lethal concentration (LC50) values with coefficents of variation (CVs) of 15.8 and 19.6%, respectively. Whole sediments which were moderately contaminated provided the best estimates of precision using CVs. Hyalella azteca and C. tentans tests in moderately contaminated sediments exhibited LC50 CVs of 38.9 and 13.5%, respectively. The CV for C. tentans growth was 31.9%. Only 3% (1 of 28) of samples exceeded acceptable interlaboratory precision limits for the H. azteca survival tests. No samples exceeded the intralaboratory precision limit for H. azteca or C. tentans survival tests. However, intralaboratory variability limits for C. tentans growth were exceeded by 80 and 100% of the laboratories for a moderately toxic and control sample, respectively. Interlaboratory variability limits for C. tentans survival were not exceeded by any laboratory. The results showed these test methods to have relatively low variance and acceptable levels of precision in interlaboratory comparisons.

Environmental Toxicology and Chemistry↗

Acute toxicity of three fire-retardant and two fire-suppressant foam formulations to the early life stages of rainbow trout ( Oncorhynchus mykiss )

Laboratory studies were conducted with five early life stages of rainbow trout, Oncorhynchus mykiss , to determine the acute toxicities of five fire-fighting chemical formulations in standardized soft and hard water. Eyed egg, embryo–larvae, swim-up fry, and 60- and 90-d posthatch juveniles were exposed to three fire retardants (Fire-Trol LCG-R, Fire-Trol GTS-R, and Phos-Chek D75-F) and two fire-suppressant foams (Phos-Chek WD-881 and Silv-Ex). Swim-up fry were generally the most sensitive life stage, whereas the eyed-egg was the least sensitive. Toxicity of fire-fighting formulations was greater in hard water than in soft water for all life stages tested with Fire-Trol GTS-R and Silv-Ex and for 90-d-old juveniles tested with Fire-Trol LCG-R. The fire-suppressant foams were more toxic than the fire retardants. The 96-h median lethal concentrations (LC50s) were ranked from the most toxic to the least toxic formulation as follows (ranges are the lowest and highest 96-h LC50 calculated for each formulation): Phos-Chek WD-881 (11–44 mg/L), Silv-Ex (11–78 mg/L), Phos-Chek D75-F (218–>3,600 mg/L), Fire-Trol GTS-R (207–>6,000 mg/L), and Fire-Trol LCG-R (872–>10,000 mg/L). Toxicity values suggest that accidental entry of fire-fighting chemicals into aquatic environments could adversely affect fish populations.

Environmental Toxicology and Chemistry↗

Small mammal populations in Maryland meadows during four years of herbicide (brominal®) applications

The herbicide Brominal® was applied at the recommended rate to one plot in each of three paired 0.6-ha plots; the other three plots were used as controls. Plots were sprayed once in the fall of 1988 and 1989 and twice in the spring of 1990 and 1991. Small mammals were trapped three times during each activity season (April-October) to obtain population estimates before and after spraying and in the spring preceding fall spraying or the fall following spring spraying. Population estimates immediately after spraying gave no evidence of direct mortality. By 1991, dicot vegetation on treated plots was suppressed and mean numbers of meadow voles (Microtus pennsylvanicus) were less than on control plots. Because meadow voles favor dicots over monocots in their diet, reduced availability of dicots may have been related to the smaller vole population estimates. Species diversity of small mammals was negatively correlated with size of vole populations, but was not different between treated and control plots. Brominal apparently induced opaque corneas in nine voles. The condition was found in two voles too small to have been conceived at the time of the last previous spray nearly 8 months earlier, suggesting exposure to residue alone.

Environmental Toxicology and Chemistry↗

A comparison of β-adrenoceptors and muscarinic cholinergic receptors in tissues of brown bullhead catfish ( Ameiurus nebulosus ) from the black river and old woman creek, Ohio

β-Adrenoceptors (βARs) and muscarinic cholinergic receptors were measured in brain, gill, and heart tissues of brown bullhead catfish exposed to polycyclic aromatic hydrocarbons in the Black River, Ohio, USA, and were compared to values from Old Woman Creek, Ohio, a reference site. A decreased number of βARs were found in the gill from Black River fish, possibly indicating a compensatory response subsequent to chemical stress.

Environmental Toxicology and Chemistry↗

A resource conservative procedure for comparison of dose-response relationships

The evaluation of effects of toxicants on a wildlife community can be complicated by varying responses among the community's constituent populations. Even within populations, considerable variability in dose-response relations may result from different avenues of exposure to the toxicant. Full-scale investigations of the dose-response relations among a variety of species and avenues of exposure can therefore be prohibitively expensive, whether this expense is measured by the number of experimental animals needed, by the human resources committed to the study, or by laboratory expenses. We propose an abbreviated protocol for investigations of multiple dose-response relations that is designed to limit these expenses. The protocol begins with the judicious choice of a baseline dose-response relation to be estimated by a full-scale study involving a minimum of five doses levels, with 10 subjects per dose level. This relation is then used as the basis for rapid screening of subsequent dose-response relations, which are compared to the baseline relation by testing for differences in the median effective dosages. These secondary studies can consist of as few as 14 animals exposed to the estimated median lethal concentration from the baseline study. We describe MS-DOS-compatible software available from the authors that can be used to analyze these data.

Environmental Toxicology and Chemistry↗

The role of water ventilation and sediment ingestion in the uptake of benzo[A]pyrene in gizzard shad ( Dorosoma cepedianum )

The objective of this study was to determine whether sediment ingestion or water ventilation was the primary route of uptake for benzo[ a ]pyrene (B a P) in the gizzard shad ( Dorosoma cepedianum ), a detritivorous fish. Two experiments were conducted in which fish were exposed to sediments spiked with 1 μg/g B a P. In the first experiment, fish were prevented from feeding by esophagus ligation. In the second experiment, 20 nonligated fish and 30 ligated fish were added to the aquarium. The nonligated fish roiled the water as they fed. Fish were collected 4, 8, 15, and 22 d after the experiments began. Gizzard shad metabolize B a P; therefore, the concentrations of B a P equivalents (parent B a P plus metabolite) were determined. Concentrations of B a P equivalents were significantly greater in the ligated fish in experiment 2 relative to those in experiment 1. In contrast, the concentration of B a P equivalents in the ligated fish in experiment 2 was not significantly different than that in the nonligated fish. Our results suggest that ventilation of turbid water may be a significant source of B a P for gizzard shad. Sediment ingestion, however, does not appear to significantly influence the total body concentration of B a P equivalents in gizzard shad.

Environmental Toxicology and Chemistry↗