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Flow-through bioassay for measuring bioaccumulation of toxic substances from sediment

Over 10 million cubic meters of sediment are dredged annually from Great Lakes waterways. Because much of this material is taken from harbors, connecting channels, and other nearshore areas that often are contaminated with toxic substances, the sediments proposed for dredging need to be evaluated for the presence of bioavailable contaminants and the potential for toxicity to the biota. Sound decisions on the appropriate disposal of the dredged material can be made only after such an evaluation. Presently, no standardized procedure exists for evaluating dredged material in freshwater systems although current criteria for discharge of dredged material into marine water have been developed (USEPA/CE 1977). In the ocean discharge guideline, it is recommended that bioassays be conducted on liquid, solid, and suspended particulate phases of dredged material. because it appears that the solid phase has the greatest potential for environmental damage and because measurement of bioaccumulation must be made to evaluate sediments for disposal (USEPA/CE 1977, Seeyle and Mac 1983), we developed a bioassay for testing the solid phase of dredged material that measures the survival of organisms and, perhaps more important, the bioaccumulation of toxic substances by aquatic organisms from naturally contaminated sediments (Peddicord et al. 1980; Rubinstein et al. 1980, 1983; Seeyle st al. 1982), several have used testing methods that result in unacceptable mortality to control organisms (Bahnick et al. 1981, Prater et al. 1983). Our bioassay is intended to estimate the potential for bioaccumlation of contaminants from sediments that are not acutely toxic to test organisms, but are suspected of containing persistent contaminants. By using test organisms that are not highly susceptible to toxic compounds, the bioaccumulation test allows estimation of the potential food-chain accumulation of contaminants that may occur in local biota from surficial sediments. In practice, bioaccumulation observed in this bioassay by organisms exposed to test sediments (sediments to be dredged) would be compared to bioaccumulation observed from sediments collected from a reference site (e.g. a disposal site or open lake), and also from control sediments (relatively clean sediment). Decisions could then be based on a comparison of results between tests and reference sediments to determine if disposal would cause dehydration to the habitat, and between reference and control sediment to determine if even the reference material is seriously contaminated. Although the test is not intended to be a toxicity test per se, use of test, reference, and control sediments enables interpretation of any mortality of organisms that may occur during the bioassays. High mortality in bioassays with test or reference sediment would indicate acute toxicity of sediments in the project area. However if high mortality occurs in all three sediments, it can be assumed that the organisms were not in a healthy state at the time of testing. We describe the results of 10-day sediment bioassays in which both mortality and bioaccumulation were measured in four aquatic organisms. We exposed two infaunal organisms and two species of fish to test and control sediments in the laboratory.

Report

Toxicity of carbon nanotubes to freshwater aquatic invertebrates

Carbon nanotubes (CNTs) are hydrophobic in nature and thus tend to accumulate in sediments if released into aquatic environments. As part of our overall effort to examine the toxicity of carbon-based nanomaterials to sediment-dwelling invertebrates, we have evaluated the toxicity of different types of CNTs in 14-d water-only exposures to an amphipod ( Hyalella azteca ), a midge ( Chironomus dilutus ), an oligochaete ( Lumbriculus variegatus ), and a mussel ( Villosa iris ) in advance of conducting whole-sediment toxicity tests with CNTs. The results of these toxicity tests conducted with CNTs added to water showed that 1.00g/L (dry wt) of commercial sources of CNTs significantly reduced the survival or growth of the invertebrates. Toxicity was influenced by the type and source of the CNTs, by whether the materials were precleaned by acid, by whether sonication was used to disperse the materials, and by species of the test organisms. Light and electron microscope imaging of the surviving test organisms showed the presence of CNTs in the gut as well as on the outer surface of the test organisms, although no evidence was observed to show penetration of CNTs through cell membranes. The present study demonstrated that both the metals solubilized from CNTs such as nickel and the "metal-free" CNTs contributed to the toxicity.

Environmental Toxicology and Chemistry

Expanding metal mixture toxicity models to natural stream and lake invertebrate communities

A modeling approach that was used to predict the toxicity of dissolved single and multiple metals to trout is extended to stream benthic macroinvertebrates, freshwater zooplankton, and Daphnia magna . The approach predicts the accumulation of toxicants (H, Al, Cd, Cu, Ni, Pb, and Zn) in organisms using 3 equilibrium accumulation models that define interactions between dissolved cations and biological receptors (biotic ligands). These models differ in the structure of the receptors and include a 2-site biotic ligand model, a bidentate biotic ligand or 2-pKa model, and a humic acid model. The predicted accumulation of toxicants is weighted using toxicant-specific coefficients and incorporated into a toxicity function called Tox, which is then related to observed mortality or invertebrate community richness using a logistic equation. All accumulation models provide reasonable fits to metal concentrations in tissue samples of stream invertebrates. Despite the good fits, distinct differences in the magnitude of toxicant accumulation and biotic ligand speciation exist among the models for a given solution composition. However, predicted biological responses are similar among the models because there are interdependencies among model parameters in the accumulation–Tox models. To illustrate potential applications of the approaches, the 3 accumulation–Tox models for natural stream invertebrates are used in Monte Carlo simulations to predict the probability of adverse impacts in catchments of differing geology in central Colorado (USA); to link geology, water chemistry, and biological response; and to demonstrate how this approach can be used to screen for potential risks associated with resource development.

Environmental Toxicology and Chemistry

Acute and chronic toxicity of sodium sulfate to four freshwater organisms in water-only exposures

The acute and chronic toxicity of sulfate (tested as sodium sulfate) was determined in diluted well water (hardness of 100 mg/L and pH 8.2) with a cladoceran ( Ceriodaphnia dubia ; 2-d and 7-d exposures), a midge ( Chironomus dilutus ; 4-d and 41-d exposures), a unionid mussel (pink mucket, Lampsilis abrupta ; 4-d and 28-d exposures), and a fish (fathead minnow, Pimephales promelas ; 4-d and 34-d exposures). Among the 4 species, the cladoceran and mussel were acutely more sensitive to sulfate than the midge and fathead minnow, whereas the fathead minnow was chronically more sensitive than the other 3 species. Acute-to-chronic ratios ranged from 2.34 to 5.68 for the 3 invertebrates but were as high as 12.69 for the fish. The fathead minnow was highly sensitive to sulfate during the transitional period from embryo development to hatching in the diluted well water, and thus, additional short-term (7- to 14-d) sulfate toxicity tests were conducted starting with embryonic fathead minnow in test waters with different ionic compositions at a water hardness of 100 mg/L. Increasing chloride in test water from 10 mg Cl/L to 25 mg Cl/L did not influence sulfate toxicity to the fish, whereas increasing potassium in test water from 1mg K/L to 3mg K/L substantially reduced the toxicity of sulfate. The results indicate that both acute and chronic sulfate toxicity data, and the influence of potassium on sulfate toxicity to fish embryos, need to be considered when environmental guidance values for sulfate are developed or refined.

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

Acute toxicity of fire-retardant and foam-suppressant chemicals to yalella azteca (Saussure)

Acute toxicity tests were conducted with Hyalella azteca Saussure (an amphipod) exposed in soft and hard waters to three fire retardants (Fire-Trol GTS-R, Fire-Trol LCG-R, and Phos-Chek D75-F) and two foam suppressants (Phos-Chek WD-881 and Silv-Ex). The chemicals were slightly to moderately toxic to amphipods. The most toxic chemical to amphipods in soft and hard water was Phos-Chek WD-881 (96-h mean lethal concentration [LC50] equal to 10 mg/L and 22 mg/L, respectively), and the least toxic chemical to amphipods in soft water was Fire-Trol GTS-R (96-h LC50 equal to 127 mg/L) and in hard water was Fire-Trol LCG-R (96-h LC50 equal to 535 mg/L). Concentrations of ammonia in tests with the three fire retardants and both water types were greater than reported LC50 values and probably were the major toxic component. Estimated un-ionized ammonia concentrations near the LC50 were frequently less than the reported LC50 ammonia concentrations for amphipods. The three fire retardants were more toxic in soft water than in hard water even though ammonia and un-ionized ammonia concentrations were higher in hard water tests than in soft water tests. The accidental entry of fire-fighting chemicals into aquatic environments could adversely affect aquatic invertebrates, thereby disrupting ecosystem function.

Environmental Toxicology and Chemistry

Development and application of a marine sediment pore-water toxicity test using Ulva fasciata zoospores

An acute (96 h) pore-water toxicity test protocol using germination and growth of Ulva fasciata zoospores as endpoints was developed to test the toxicity of marine and estuarine sediment pore-water samples. Tests with an organic toxicant (sodium dodecyl sulfate; SDS), three metals (Cd, Cu, and Zn), and ammonia (NH 3 ) were conducted to determine zoospore sensitivity. Zoospore germination and gametophyte growth were as sensitive to SDS as sea urchin ( Arbacia punctulata ) fertilization and embryological development. Zoospore sensitivity to metals was greater than or comparable to that of adult macroalgae. Zoospores were less sensitive to NH 3 than were other commonly used toxicity test organisms. Test results using this algal assay with sediment pore-water samples with high NH 3 concentrations were compared with results from sea urchin fertilization and embryological development tests for the same samples. Ulva fasciata zoospore germination was not affected by samples with high NH 3 concentrations that were toxic in both sea urchin tests. Zoospore tolerance of NH 3 and sensitivity to other contaminants indicate that their response may be useful in toxicity identification evaluation studies with pore-water samples that contain high concentrations of unionized NH 3 .

Environmental Toxicology and Chemistry

Toxicity of inorganic contaminants, individually and in environmental mixtures, to three endangered fishes (Colorado squawfish, bonytail, and razorback sucker)

Two life stages of three federally-listed endangered fishes, Colorado squawfish ( Ptychocheilus lucius ), bonytail ( Gila elegans ), and razorback sucker ( Xyrauchen texanus ) were exposed to copper, selenate, selenite, and zinc individually, and to mixtures of nine inorganics in a reconstituted water that simulated the water quality of the middle Green River, Utah. The mixtures simulated environmental ratios of arsenate, boron, copper, molybdenum, selenate, selenite, uranium, vanadium, and zinc in two tributaries, Ashley Creek and Stewart Lake outlet, of the middle Green River. The rank order of toxicity of the individual inorganics, from most to least toxic, was: copper > zinc > selenite > selenate. Colorado squawfish larvae were more sensitive to all four inorganics and the two mixtures than the juveniles, whereas there was no consistent response between the two life stages for the other two species. There was no consistent difference in sensitivity to the inorganics among the three endangered fishes. Both mixtures exhibited either additive or greater than additive toxicity to these fishes. The primary toxic components in the mixtures, based on toxic units, were copper and zinc. Acute toxicity values were compared to measured environmental concentrations in the two tributaries to derive margins of uncertainty. Margins of uncertainty were low for both mixtures (9–22 for the Stewart Lake outlet mixture, and 12–32 for the Ashley Creek mixture), indicating that mixtures of inorganics derived from irrigation activities may pose a hazard to endangered fishes in the Green River.

Archives of Environmental Contamination and Toxico

Acute toxicity and hazard assessment of Rodeo®, X-77 Spreader®, and Chem-Trol® to aquatic invertebrates

The herbicide Rodeo ® provides waterfowl managers with an effective chemical tool for creating open water habitats in wetlands if its use does not adversely affect native invertebrate communities. The survival of caged Chironomus spp. (midge), Hyalella azteca (amphipod), Stagnicola elodes (pond snail), and Nephelopsis obscura (leech) was assessed in prairie pothole wetlands treated by air with a tank mixture of Rodeo ® , the surfactant X-77 Spreader ® , and the drift retardant Chem-Trol ® at a rate recommended for controlling cattails. Laboratory studies were then conducted to determine the acute toxicities of Rodeo ® , X-77 Spreader ® , and Chem-Trol ® , individually and in simulated tank mixtures, to the same invertebrates and to Daphnia magna in reconstituted water representative of these wetlands. There was no difference in the survival of caged invertebrates between treated and reference wetlands after 21 days. Based on nominal concentrations of the formulations, X-77 Spreader ® (LC50s=2.0–14.1 mg/L) was about 83–136 times more toxic than Rodeo ® (LC50s=218–1216 mg/L) to aquatic invertebrates. Chem-Trol ® killed ≤10% of the animals at 10,000 mg/L and ≤50% of the animals at 28,000 mg/L. Daphnia magna were more sensitive than the other species to X-77 Spreader ® , Rodeo ® , and the simulated Rodeo ® tank mixture (RTM). The joint toxic action of the RTM was additive for amphipods and midges, greater than additive for leeches, and was less than additive for daphnids. X-77 Spreader ® was the major toxic component in the RTM. Binary mixtures of X-77 Spreader ® , Rodeo ® , and Chem-Trol ® at tank mixture and equitoxic ratios also showed additive toxicity to amphipods. The use of Rodeo ® (applied as a tank mixture with X-77 Spreader ® and Chem-Trol ® ) as a management tool in wetlands does not pose an acute hazard to native aquatic invertebrates because the concentrations of Rodeo ® , X-77 Spreader ® , and Chem-Trol ® found to be acutely toxic to these invertebrates were much higher than their expected or measured concentrations in water from wetlands treated with the RTM.

Archives of Environmental Contamination and Toxico

Assessing contaminant sensitivity of endangered and threatened aquatic species: Part I. Acute toxicity of five chemicals

Assessment of contaminant impacts to federally identified endangered, threatened and candidate, and state-identified endangered species (collectively referred to as "listed" species) requires understanding of a species' sensitivities to particular chemicals. The most direct approach would be to determine the sensitivity of a listed species to a particular contaminant or perturbation. An indirect approach for aquatic species would be application of toxicity data obtained from standard test procedures and species commonly used in laboratory toxicity tests. Common test species (fathead minnow, Pimephales promelas; sheepshead minnow, Cyprinodon variegatus; and rainbow trout, Oncorhynchus mykiss) and 17 listed or closely related species were tested in acute 96-hour water exposures with five chemicals (carbaryl, copper, 4-nonylphenol, pentachlorophenol, and permethrin) representing a broad range of toxic modes of action. No single species was the most sensitive to all chemicals. For the three standard test species evaluated, the rainbow trout was more sensitive than either the fathead minnow or sheepshead minnow and was equal to or more sensitive than listed and related species 81% of the time. To estimate an LC50 for a listed species, a factor of 0.63 can be applied to the geometric mean LC50 of rainbow trout toxicity data, and more conservative factors can be determined using variance estimates (0.46 based on 1 SD of the mean and 0.33 based on 2 SD of the mean). Additionally, a low- or no-acute effect concentration can be estimated by multiplying the respective LC50 by a factor of approximately 0.56, which supports the United States Environmental Protection Agency approach of multiplying the final acute value by 0.5 (division by 2). When captive or locally abundant populations of listed fish are available, consideration should be given to direct testing. When direct toxicity testing cannot be performed, approaches for developing protective measures using common test species toxicity data are available. ?? 2005 Springer Science+Business Media, Inc.

Archives of Environmental Contamination and Toxico

Aquatic toxicity of chemical road dust suppressants to freshwater organisms

Unpaved roads make up at least 14 million kilometers of the worldwide road network. Although investigations of road runoff often are focused on paved roads, unpaved roads contribute large volumes of runoff to roadside aquatic habitats and introduce unique constituents to runoff, such as chemical dust suppressants. At least 200 products across five chemical categories are commercially available for road dust suppression and are typically applied at rates up to 4.5 L/m 2 . Many of these products are poorly described and are lacking basic information on environmental transport, fate, and potential toxicity to roadside organisms. We characterized the aquatic toxicity of 27 commercially available dust control products, including 13 biobased products from the U.S. Department of Agriculture BioPreferred catalog, using juvenile rainbow trout. Acute toxicity varied by more than 1000-fold among products, with 96-h LC50 values ranging from 1.7 to > 16,000 mg/L. Toxicity was not well-predicted by product category. Testing with selected products after simulated weathering under UV radiation did not provide evidence of photoenhanced toxicity. Additional tests with freshwater mussels, juvenile crayfish, pond snails, and amphibian larvae indicated that juvenile rainbow trout were reasonable surrogates for these organisms for a subset of products. This effort represents one of the first comparative studies of dust suppressant toxicity and provides important information for assessing risk to aquatic resources from a widely used but understudied class of contaminants in road runoff.

Archives of Environmental Contamination and Toxico

Toxicity of manganese to Ceriodaphnia dubia and Hyalella azteca

Manganese is a toxic element frequently overlooked when assessing toxicity of effluents, sediments, and pore waters. Manganese can be present at toxic levels in anoxic solutions due to increased solubility under chemically reducing conditions, and it can remain at those levels for days in aerated test waters due to slow precipitation kinetics. Ceriodaphnia dubia and Hyalella azteca are freshwater organisms often used for toxicity testing and recommended for assessments of effluents and pore waters. Lethal and reproductive-inhibition concentrations of Mn were determined for C. dubia in acute 48-h tests and chronic three-brood tests using animals <24 h old and between 24 and 48 h old. Sensitivity of H. azteca to Mn was determined with 7-day-old animals in acute 96-h tests. Tests were run at three levels of water hardness to assess the amelioratory effect, which was often significant. Manganese concentrations were measured analytically at test initiation and after 96 h for calculation of toxicity and determination of Mn precipitation during the tests. Minimal amounts of Mn (≤3%) precipitated within 96 h. LC 50 s determined for H. azteca progressively increased from 3.0 to 8.6 to 13.7 mg Mn/L in soft, moderately hard, and hard waters, respectively. The tolerance of C. dubia to Mn was not significantly different between moderately hard and hard waters, but was significantly lower in soft water. Manganese sensitivity of C. dubia was not significantly different between the ages tested. Acute LC 50 values for C. dubia averaged 6.2, 14.5 and 15.2 mg Mn/L and chronic IC 50 values averaged 3.9, 8.5 and 11.5 mg Mn/L for soft, moderately-hard and hard waters, respectively. Manganese toxicity should be considered when assessing solutions with concentrations approaching these levels.

Archives of Environmental Contamination and Toxico

Concentration addition and independent action assessments of the binary mixtures of four toxicants on zebra mussel (Dreissena polymorpha) mortality

Researchers most often focus on individual toxicants when identifying effective chemical control agents for aquatic invasive species; however, toxicant mixtures may elicit synergistic effects. Synergistic effects may decrease required concentrations and shorten exposure durations for treatments. We investigated four toxicants (EarthTec QZ, Clam-Trol CT-2, niclosamide, and potassium chloride) that have been considered to control invasive zebra mussels ( Dreissena polymorpha Pallas, 1771). We determined the toxicity of binary mixtures for five different mixture ratios to adult mussels. We compared our observations to predictions made with concentration addition and independent action paradigms, as based on the dose-response relationships of each individual toxicant. We calculated the model deviation ratio for each combination at the LC 50 and LC 90 and identified three possible interactions: synergy, antagonism, and additivity. We found that mixtures of niclosamide and Clam-Trol CT-2 were the most synergistic while mixtures that included potassium chloride were largely additive to antagonistic. The use of synergistic combinations has potential to decrease the overall volume and concentration of individual toxicants required for dreissenid mussel treatments, thereby decreasing cost.

Aquatic Toxicology

Blooms of the toxic dinoflagellate Alexandrium fundyense in the western Gulf of Maine in 1993 and 1994: A comparative modeling study

Blooms of the toxic dinoflagellate Alexandrium fundyense commonly occur in the western Gulf of Maine but the amount of toxin observed in coastal shellfish is highly variable. In this study, a coupled physical-biological model is used to investigate the dynamics underlying the observed A. fundyense abundance and shellfish toxicity in 1993 (a high toxicity year) and 1994 (low toxicity year). The physical model simulates the spring circulation, while the biological model estimates the germination and population dynamics of A. fundyense based on laboratory and field data. The model captures the large-scale aspects of the initiation and development of A. fundyense blooms during both years, but small-scale patchiness and the dynamics of bloom termination remain problematic. In both cases, the germination of resting cysts accounts for the magnitude of A. fundyense populations early in the spring. Simulations with low net A. fundyense growth rates capture the mean observed concentration during the bloom peak, which is of similar magnitude during both years. There is little evidence that large-scale changes in biological dynamics between 1993 and 1994 were a primary driver of the differences in shellfish toxicity. Results instead suggest that the persistent southwesterly flow of the western Maine Coastal Current led to A. fundyense populations of similar alongshore extent by late May of both years. This period coincides with peak cell abundance in the region. Variations in wind forcing (downwelling favorable in 1993, upwelling favorable in 1994) and subsequent cell transport (inshore in 1993, offshore in 1994) in early June then provides a plausible explanation for the dramatic mid-June differences in shellfish toxicity throughout the western Gulf of Maine. ?? 2007 Elsevier Ltd. All rights reserved.

Continental Shelf Research

Acute toxicity of diphacinone in Northern bobwhite: Effects on survival and blood clotting

The anticoagulant rodenticide diphacinone was slightly toxic (acute oral LD 50 2014 mg/kg) to Northern bobwhite ( Colinus virginianus ) in a 14-day acute toxicity trial. Precise and sensitive assays of blood clotting (prothrombin time, Russell’s Viper venom time, and thrombin clotting time) were adapted for use in quail, and this combination of assays is recommended to measure the effects of anticoagulant rodenticides. A single oral sublethal dose of diphacinone (434 mg/kg body weight) prolonged clotting time at 48 h post-dose compared to controls. At 783 mg/kg (approximate LD 02 ), clotting time was prolonged at both 24 and 48 h post-dose. Prolongation of in vitro clotting time reflects impaired coagulation complex activity, and was detected before overt signs of toxicity were apparent at the greatest dosages (2868 and 3666 mg/kg) in the acute toxicity trial. These clotting time assays and toxicity data will assist in the development of a pharmacodynamic model to predict toxicity, and also facilitate rodenticide hazard and risk assessments in avian species.

Ecotoxicology and Environmental Safety

Disentangling the effects of low pH and metal mixture toxicity on macroinvertebrate diversity

One of the primary goals of biological assessment of streams is to identify which of a suite of chemical stressors is limiting their ecological potential. Elevated metal concentrations in streams are often associated with low pH, yet the effects of these two potentially limiting factors of freshwater biodiversity are rarely considered to interact beyond the effects of pH on metal speciation. Using a dataset from two continents, a biogeochemical model of the toxicity of metal mixtures (Al, Cd, Cu, Pb, Zn) and quantile regression, we addressed the relative importance of both pH and metals as limiting factors for macroinvertebrate communities. Current environmental quality standards for metals proved to be protective of stream macroinvertebrate communities and were used as a starting point to assess metal mixture toxicity. A model of metal mixture toxicity accounting for metal interactions was a better predictor of macroinvertebrate responses than a model considering individual metal toxicity. We showed that the direct limiting effect of pH on richness was of the same magnitude as that of chronic metal toxicity, independent of its influence on the availability and toxicity of metals. By accounting for the direct effect of pH on macroinvertebrate communities, we were able to determine that acidic streams supported less diverse communities than neutral streams even when metals were below no-effect thresholds. Through a multivariate quantile model, we untangled the limiting effect of both pH and metals and predicted the maximum diversity that could be expected at other sites as a function of these variables. This model can be used to identify which of the two stressors is more limiting to the ecological potential of running waters.

Environmental Pollution

Influence of sediment chemistry and sediment toxicity on macroinvertebrate communities across 99 wadable streams of the Midwestern USA

Simultaneous assessment of sediment chemistry, sediment toxicity, and macroinvertebrate communities can provide multiple lines of evidence when investigating relations between sediment contaminants and ecological degradation. These three measures were evaluated at 99 wadable stream sites across 11 states in the Midwestern United States during the summer of 2013 to assess sediment pollution across a large agricultural landscape. This evaluation considers an extensive suite of sediment chemistry totaling 274 analytes (polycyclic aromatic hydrocarbons, organochlorine compounds, polychlorinated biphenyls, polybrominated diphenyl ethers, trace elements, and current-use pesticides) and a mixture assessment based on the ratios of detected compounds to available effects-based benchmarks. The sediments were tested for toxicity with the amphipod Hyalella azteca (28-d exposure), the midge Chironomus dilutus (10-d), and, at a few sites, with the freshwater mussel Lampsilis siliquoidea (28-d). Sediment concentrations, normalized to organic carbon content, infrequently exceeded benchmarks for aquatic health, which was generally consistent with low rates of observed toxicity. However, the benchmark-based mixture score and the pyrethroid insecticide bifenthrin were significantly related to observed sediment toxicity. The sediment mixture score and bifenthrin were also significant predictors of the upper limits of several univariate measures of the macroinvertebrate community (EPT percent, MMI (Macroinvertebrate Multimetric Index) Score, Ephemeroptera and Trichoptera richness) using quantile regression. Multivariate pattern matching (Mantel-like tests) of macroinvertebrate species per site to identified contaminant metrics and sediment toxicity also indicate that the sediment mixture score and bifenthrin have weak, albeit significant, influence on the observed invertebrate community composition. Together, these three lines of evidence (toxicity tests, univariate metrics, and multivariate community analysis) suggest that elevated contaminant concentrations in sediments, in particular bifenthrin, is limiting macroinvertebrate communities in several of these Midwest streams.

Science of the Total Environment

Daily stream samples reveal highly complex pesticide occurrence and potential toxicity to aquatic life

Transient, acutely toxic concentrations of pesticides in streams can go undetected by fixed-interval sampling programs. Here we compare temporal patterns in occurrence of current-use pesticides in daily composite samples to those in weekly composite and weekly discrete samples of surface water from 14 small stream sites. Samples were collected over 10–14 weeks at 7 stream sites in each of the Midwestern and Southeastern United States. Samples were analyzed for over 200 pesticides and degradates by direct aqueous injection liquid chromatography with tandem mass spectrometry. Nearly 2 and 3 times as many unique pesticides were detected in daily samples as in weekly composite and weekly discrete samples, respectively. Based on exceedances of acute-invertebrate benchmarks (AIB) and(or) a Pesticide Toxicity Index (PTI) >1, potential acute-invertebrate toxicity was predicted at 11 of 14 sites from the results for daily composite samples, but was predicted for only 3 sites from weekly composites and for no sites from weekly discrete samples. Insecticides were responsible for most of the potential invertebrate toxicity, occurred transiently, and frequently were missed by the weekly discrete and composite samples. The number of days with benthic-invertebrate PTI ≥0.1 in daily composite samples was inversely related to Ephemeroptera, Plecoptera, and Trichoptera (EPT) richness at the sites. The results of the study indicate that short-term, potentially toxic peaks in pesticides frequently are missed by weekly discrete sampling, and that such peaks may contribute to degradation of invertebrate community condition in small streams. Weekly composite samples underestimated maximum concentrations and potential acute-invertebrate toxicity, but to a lesser degree than weekly discrete samples, and provided a reasonable approximation of the 90th percentile total concentrations of herbicides, insecticides, and fungicides, suggesting that weekly composite sampling may be a compromise between assessment needs and cost.

Science of the Total Environment