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Organochlorine contaminants in fishes from coastal waters west of Amukta Pass, Aleutian Islands, Alaska, USA

Organochlorines were examined in liver and stable isotopes in muscle of fishes from the western Aleutian Islands, Alaska, in relation to islands or locations affected by military occupation. Pacific cod (Gadus macrocephalus) , Pacific halibut (Hippoglossus stenolepis) , and rock greenling (Hexagrammos lagocephalus) were collected from nearshore waters at contemporary (decommissioned) and historical (World War II) military locations, as well as at reference locations. Total (Σ) polychlorinated biphenyls (PCBs) dominated the suite of organochlorine groups (ΣDDTs, Σchlordane cyclodienes, Σother cyclodienes, and Σchlorinated benzenes and cyclohexanes) detected in fishes at all locations, followed by ΣDDTs and Σchlordanes; dichlorodiphenyldi-chloroethylene ( p , p ′DDE) composed 52 to 66% of ΣDDTs by species. Organochlorine concentrations were higher or similar in cod compared to halibut and lowest in greenling; they were among the highest for fishes in Arctic or near Arctic waters. Organochlorine group concentrations varied among species and locations, but ΣPCB concentrations in all species were consistently higher at military locations than at reference locations. Moreover, all organochlorine group concentrations were higher in halibut from military locations than those from reference locations. A wide range of molecular weight organochlorines was detected at all locations, which implied regional or long-range transport and deposition, as well as local point-source contamination. Furthermore, a preponderance of higher-chlorinated PCB congeners in fishes from contemporary military islands implied recent exposure. Concentrations in all organochlorine groups increased with δ 15 N enrichment in fishes, and analyses of residual variation provided further evidence of different sources of ΣPCBs and p , p ′DDE among species and locations.

Alaska↗

Regression models for explaining and predicting concentrations of organochlorine pesticides in fish from streams in the United States

Empirical regression models were developed for estimating concentrations of dieldrin, total chlordane, and total DDT in whole fish from U.S. streams. Models were based on pesticide concentrations measured in whole fish at 648 stream sites nationwide (1992-2001) as part of the U.S. Geological Survey's National Water Quality Assessment Program. Explanatory variables included fish lipid content, estimates (or surrogates) representing historical agricultural and urban sources, watershed characteristics, and geographic location. Models were developed using Tobit regression methods appropriate for data with censoring. Typically, the models explain approximately 50 to 70% of the variability in pesticide concentrations measured in whole fish. The models were used to predict pesticide concentrations in whole fish for streams nationwide using the U.S. Environmental Protection Agency's River Reach File 1 and to estimate the probability that whole-fish concentrations exceed benchmarks for protection of fish-eating wildlife. Predicted concentrations were highest for dieldrin in the Corn Belt, Texas, and scattered urban areas; for total chlordane in the Corn Belt, Texas, the Southeast, and urbanized Northeast; and for total DDT in the Southeast, Texas, California, and urban areas nationwide. The probability of exceeding wildlife benchmarks for dieldrin and chlordane was predicted to be low for most U.S. streams. The probability of exceeding wildlife benchmarks for total DDT is higher but varies depending on the fish taxon and on the benchmark used. Because the models in the present study are based on fish data collected during the 1990s and organochlorine pesticide residues in the environment continue to decline decades after their uses were discontinued, these models may overestimate present-day pesticide concentrations in fish. ?? 2009 SETAC.

Environmental Toxicology and Chemistry↗

Using propensity scores to estimate the effects of insecticides on stream invertebrates from observational data

Analyses of observational data can provide insights into relationships between environmental conditions and biological responses across a broader range of natural conditions than experimental studies, potentially complementing insights gained from experiments. However, observational data must be analyzed carefully to minimize the likelihood that confounding variables bias observed relationships. Propensity scores provide a robust approach for controlling for the effects of measured confounding variables when analyzing observational data. Here, we use propensity scores to estimate changes in mean invertebrate taxon richness in streams that have experienced insecticide concentrations that exceed aquatic life use benchmark concentrations. A simple comparison of richness in sites exposed to elevated insecticides with those that were not exposed suggests that exposed sites had on average 6.8 fewer taxa compared to unexposed sites. The presence of potential confounding variables makes it difficult to assert a causal relationship from this simple comparison. After controlling for confounding factors using propensity scores, the difference in richness between exposed and unexposed sites was reduced to 4.1 taxa, a difference that was still statistically significant. Because the propensity score analysis controlled for the effects of a wide variety of possible confounding variables, we infer that the change in richness observed in the propensity score analysis was likely caused by insecticide exposure.

Environmental Toxicology and Chemistry↗

Antidepressants at environmentally relevant concentrations affect predator avoidance behavior of larval fathead minnows (Pimephales promelas).

The effects of embryonic and larval exposure to environmentally relevant (ng/L) concentrations of common antidepressants, fluoxetine, sertraline, venlafaxine, and bupropion (singularly and in mixture) on C-start escape behavior were evaluated in fathead minnows (Pimephales promelas). Embryos (postfertilization until hatching) were exposed for 5 d and, after hatching, were allowed to grow in control well water until 12 d old. Similarly, posthatch fathead minnows were exposed for 12 d to these compounds. High-speed (1,000 frames/s) video recordings of escape behavior were collected and transferred to National Institutes of Health Image for frame-by- frame analysis of latency periods, escape velocities, and total escape response (combination of latency period and escape velocity). When tested 12 d posthatch, fluoxetine and venlafaxine adversely affected C-start performance of larvae exposed as embryos. Conversely, larvae exposed for 12 d posthatch did not exhibit altered escape responses when exposed to fluoxetine but were affected by venlafaxine and bupropion exposure. Mixtures of these four antidepressant pharmaceuticals slowed predator avoidance behaviors in larval fathead minnows regardless of the exposure window. The direct impact of reduced C-start performance on survival and, ultimately, reproductive fitness provides an avenue to assess the ecological relevance of exposure in an assay of relatively short duration.

Environmental Toxicology and Chemistry↗

A simplified method for correcting contaminant concentrations in eggs for moisture loss.

We developed a simplified and highly accurate method for correcting contaminant concentrations in eggs for the moisture that is lost from an egg during incubation. To make the correction, one injects water into the air cell of the egg until overflowing. The amount of water injected corrects almost perfectly for the amount of water lost during incubation or when an egg is left in the nest and dehydrates and deteriorates over time. To validate the new method we weighed freshly laid chicken (Gallus gallus) eggs and then incubated sets of fertile and dead eggs for either 12 or 19 d. We then injected water into the air cells of these eggs and verified that the weights after water injection were almost identical to the weights of the eggs when they were fresh. The advantages of the new method are its speed, accuracy, and simplicity: It does not require the calculation of a correction factor that has to be applied to each contaminant residue.

Environmental Toxicology and Chemistry↗

Evaluation of acute copper toxicity to juvenile freshwater mussels (fatmucket, lampsilis siliquoidea) in natural and reconstituted waters

The influence of dissolved organic carbon (DOC) and water composition on the toxicity of copper to juvenile freshwater mussels (fatmucket, Lampsilis siliquoidea ) were evaluated in natural and reconstituted waters. Acute 96‐h copper toxicity tests were conducted at four nominal DOC concentrations (0, 2.5, 5, and 10 mg/L as carbon [C]) in dilutions of natural waters and in American Society for Testing and Materials (ASTM) reconstituted hard water. Toxicity tests also were conducted in ASTM soft, moderately hard, hard, and very hard reconstituted waters (nominal hardness 45–300 mg/L as CaCO 3 ). Three natural surface waters (9.5–11 mg/L DOC) were diluted to obtain a series of DOC concentrations with diluted well water, and an extract of natural organic matter and commercial humic acid was mixed with ASTM hard water to prepare a series of DOC concentrations for toxicity testing. Median effective concentrations (EC50s) for dissolved copper varied >40‐fold (9.9 to >396 μg Cu/L) over all 21 treatments in various DOC waters. Within a particular type of DOC water, EC50s increased 5‐ to 12‐fold across DOC concentrations of 0.3 to up to 11 mg C/L. However, EC50s increased by only a factor of 1.4 (21–30 μg Cu/L) in the four ASTM waters with wide range of water hardness (52–300 mg CaCO 3 /L). Predictions from the biotic ligand model (BLM) for copper explained nearly 90% of the variability in EC50s. Nearly 70% of BLM‐normalized EC50s for fatmucket tested in natural waters were below the final acute value used to derive the U.S. Environmental Protection Agency acute water quality criterion for copper, indicating that the criterion might not be protective of fatmucket and perhaps other mussel species.

Environmental Toxicology and Chemistry↗

The Asian clam Corbicula fluminea as a biomonitor of trace element contamination: Accounting for different sources of variation using an hierarchical linear model

In the present study, specimens of the invasive clam, Corbicula fluminea, were collected above and below possible sources of potentially toxic trace elements (As, Cd, Cr, Cu, Hg, Pb, and Zn) in the Altamaha River system (Georgia, USA). Bioaccumulation of these elements was quantified, along with environmental (water and sediment) concentrations. Hierarchical linear models were used to account for variability in tissue concentrations related to environmental (site water chemistry and sediment characteristics) and individual (growth metrics) variables while identifying the strongest relations between these variables and trace element accumulation. The present study found significantly elevated concentrations of Cd, Cu, and Hg downstream of the outfall of kaolin-processing facilities, Zn downstream of a tire cording facility, and Cr downstream of both a nuclear power plant and a paper pulp mill. Models of the present study indicated that variation in trace element accumulation was linked to distance upstream from the estuary, dissolved oxygen, percentage of silt and clay in the sediment, elemental concentrations in sediment, shell length, and bivalve condition index. By explicitly modeling environmental variability, the Hierarchical linear modeling procedure allowed the identification of sites showing increased accumulation of trace elements that may have been caused by human activity. Hierarchical linear modeling is a useful tool for accounting for environmental and individual sources of variation in bioaccumulation studies. ?? 2009 SETAC.

Environmental Toxicology and Chemistry↗

Selenium bioaccumulation and body condition in shorebirds and terns breeding in San Francisco Bay, California, USA

The present study evaluated Se bioaccumulation in four waterbird species ( n = 206 birds) that breed within San Francisco Bay, California, USA: American avocets ( Recurvirostra americana ), black-necked stilts ( Himantopus mexicanus ), Forster's terns ( Sterna forsteri ), and Caspian terns ( Hydroprogne caspia ). Selenium concentrations were variable and influenced by several factors, including species, region, reproductive stage, age, and sex. Adult Se concentrations (μg/g dry wt) in livers ranged from 3.07 to 48.70 in avocets (geometric mean ± standard error, 7.92 ± 0.64), 2.28 to 41.10 in stilts (5.29 ± 0.38), 3.73 to 14.50 in Forster's terns (7.13 ± 0.38), and 4.77 to 14.40 in Caspian terns (6.73 ± 0.78). Avocets had higher Se concentrations in the North Bay compared to the South Bay, whereas stilt Se concentrations were similar between these regions and Forster's terns had lower Se concentrations in the North Bay compared to the South Bay. Female avocets had higher Se concentrations than male avocets, but this was not the case for stilts and Forster's terns. Of the factors assessed, reproductive stage had the most consistent effect among species. Prebreeding birds tended to have higher liver Se concentrations than breeding birds, but this trend was statistically significant only for Forster's terns. Forster's tern chicks had lower Se concentrations than Forster's tern adults, whereas avocet and stilt adults and chicks were similar. Additionally, body condition was negatively related to liver Se concentrations in Forster's tern adults but not in avocet, stilt, or Caspian tern adults and chicks. These variable results illustrate the complexity of Se bioaccumulation and highlight the need to sample multiple species and examine several factors to assess the impact of Se on wildlife.

Environmental Toxicology and Chemistry↗

Occurrence and accumulation of pesticides and organic contaminants in river sediment, water and clam tissues from the San Joaquin River and tributaries, California

A study was conducted in 1992 to assess the effects of anthropogenic activities and land use on the water quality of the San Joaquin River and its major tributaries. This study focused on pesticides and organic contaminants, looking at distributions of contaminants in water, bed and suspended sediment, and the bivalve Corbicula fluminea. Results indicated that this river system is affected by agricultural practices and urban runoff. Sediments from Dry Creek contained elevated concentrations of polycyclic aromatic hydrocarbons (PAHs), possibly derived from urban runoff from the city of Modesto; suspended sediments contained elevated amounts of chlordane. Trace levels of triazine herbicides atrazine and simazine were present in water at most sites. Sediments, water, and bivalves from Orestimba Creek, a westside tributary draining agricultural areas, contained the greatest levels of DDT (1,1,1-trichloro-2-2-bis[p-chlorophenyl]ethane), and its degradates DDD (1,1-dichloro-2,2-bis[p-chlorophenyl]ethane), and DDE (1,1-dichloro-2,2- bis[p-chlorophenyl]ethylene). Sediment adsorption co efficients (K(oc)), and bioconcentration factors (BCF) in Corbicula of DDT, DDD, and DDE at Orestimba Creek were greater than predicted values. Streams of the western San Joaquin Valley can potentially transport significant amounts of chlorinated pesticides to the San Joaquin River, the delta, and San Francisco Bay. Organochlorine compounds accumulate in bivalves and sediment and may pose a problem to other biotic species in this watershed.

California↗

Phytotoxicity of floodplain soils contaminated with trace metals along the clark fork river, Grant-Kohrs Ranch National Historic Site, Deer Lodge, Montana, United States

Concentrations of metals in sediments and soils deposited along the floodplain of the Clark Fork River, within the Grant-Kohrs Ranch National Historic Site, Deer Lodge, Montana, USA, have exceeded maximum background concentrations in the United States for most metals tested. As a result of mining and smelting activities, portions of the Deer Lodge Valley, including the Grant-Kohrs Ranch, have received National Priority List Designation under the Comprehensive Environmental Response, Compensation and Liability Act. Using a series of plant germination tests, pH measurements, and metal analyses, this study investigated the toxicity of soils from floodplain 'slicken' areas, bare spots devoid of vegetation, along the Clark Fork River. The slicken soils collected from the Grant-Kohrs Ranch were toxic to all four plant species tested. The most sensitive endpoint in the germination tests was root length and the least sensitive was emergence. Considering emergence, the most sensitive species was the resident grass species Agrostis gigantea. The sensitivities were reversed when root lengths were examined, with Echinochloa crusgalli showing the greatest sensitivity. Both elevated concentrations of metals and low pH were necessary to produce an acutely phytotoxic response in laboratory seed germination tests using slicken soils. Moreover, pH values on the Grant-Kohrs Ranch appear to be a better predictor of acutely phytotoxic conditions than total metal levels.

Environmental Toxicology and Chemistry↗

Tadpole swimming performance and activity affected by acute exposure to sublethal levels of carbaryl

General activity and swimming performance (i.e., sprint speed and distance) of plains leopard frog tadpoles (Rana blairi) were examined after acute exposure to three sublethal concentrations of carbaryl (3.5, 5.0, and 7.2 mg/L). Both swimming performance and spontaneous swimming activity are important for carrying out life history functions (e.g., growth and development) and for escaping from predators. Measured tadpole activity diminished by nearly 90% at 3.5 mg/L carbaryl and completely ceased at 7.2 mg/L. Sprint speed and sprint distance also decreased significantly following exposure. Carbaryl affected both swimming performance and activity after just 24 h, suggesting that 24 h may be an adequate length of exposure to determine behavioral effects on tadpoles. Slight recovery of activity levels was noted at 24 and 48 h post-exposure; no recovery of swimming performance was observed. Reduction in activity and swimming performance may result in increased predation rates and, because activity is closely associated with feeding, may result in slowed growth leading to a failure to emerge before pond drying or an indirect reduction in adult fitness. Acute exposure to sublethal toxicants such as carbaryl may not only affect immediate survival of tadpoles but also impact critical life history functions and generate changes at the local population level.

Environmental Toxicology and Chemistry↗

Rapid toxicity assessment of sediments from estuarine ecosystems: A new tandem in vitro testing approach

Microtox® and Mutatox® were used to evaluate the acute toxicity and genotoxicity, respectively, of organic sediment extracts from Pensacola Bay and St. Andrew Bay, two estuaries that cover about 273 and 127 km 2 , respectively, along the Gulf coast of Florida, USA. The sensitivity and selectivity of these two bioluminescent toxicity assays were demonstrated in validation studies with over 50 pesticides, genotoxins, and industrial pollutants, both as single compounds and in complex mixtures. The 50% effective concentration (EC50) values of insecticides, petroleum products, and polychlorinated biphenyls determined by Microtox all tended to group around the mean EC50 value of 1.2 (0.8) mg/L. The polycyclic aromatic hydrocarbon sensitivity of Mutatox was in general similar to that reported in the Ames test. Surficial sediment samples were collected, extracted with dichloromethane, evaporated and concentrated under nitrogen, dissolved in dimethyl sulfoxide, assayed for acute toxicity and genotoxicity, and compared with reference sediments. Samples with low EC50 values, and determined to be genotoxic, were detected in Massalina Bayou, Watson Bayou, East Bay, and St. Andrew Bay–East in St. Andrew Bay as well as Bayou Grande, Bayou Chico, and Bayou Texar in Pensacola Bay. An overview of these data sets analyzed by Spearman rank correlation showed a significant correlation between acute toxicity and genotoxicity ( p < 0.05). Microtox and Mutatox in tandem was a sensitive, cost‐effective, and rapid (<24 h) screening tool that identified troublesome areas of pollution and assessed the potential sediment toxicity of lipophilic contaminants in aquatic ecosystems.

Environmental Toxicology and Chemistry↗

Effect of zeolite on toxicity of ammonia in freshwater sediments: Implications for toxicity identification evaluation procedures

Techniques for reducing ammonia toxicity in freshwater sediments were investigated as part of a project to develop toxicity identification and evaluation (TIE) procedures for whole sediments. Although ammonia is a natural constituent of freshwater sediments, pollution can lead to ammonia concentrations that are toxic to benthic invertebrates, and ammonia can also contribute to the toxicity of sediments that contain more persistent contaminants. We investigated the use of amendments of a natural zeolite mineral, clinoptilolite, to reduce concentrations of ammonia in sediment pore water. Zeolites have been widely used for removal of ammonia in water treatment and in aqueous TIE procedures. The addition of granulated zeolite to ammonia-spiked sediments reduced pore-water ammonia concentrations and reduced ammonia toxicity to invertebrates. Amendments of 20% zeolite (v/v) reduced ammonia concentrations in pore water by ???70% in spiked sediments with ammonia concentrations typical of contaminated freshwater sediments. Zeolite amendments reduced toxicity of ammonia-spiked sediments to three taxa of benthic invertebrates (Hyalella azteca, Lumbriculus variegatus, and Chironomus tentans), despite their widely differing sensitivity to ammonia toxicity. In contrast, zeolite amendments did not reduce acute toxicity of sediments containing high concentrations of cadmium or copper or reduce concentrations of these metals in pore waters. These studies suggest that zeolite amendments, used in conjunction with toxicity tests with sensitive taxa such as H. azteca, may be an effective technique for selective reduction of ammonia toxicity in freshwater sediments.

Environmental Toxicology and Chemistry↗

Health status and relative exposure of mule deer and white-tailed deer to soil contaminants at the rocky mountain arsenal

We evaluated the health of 18 radio-collared deer [13 mule deer ( Odocoileus hemionus ) and 5 white-tailed deer ( O. virginianus )] from the Rocky Mountain Arsenal, near Denver, Colorado, USA, a Superfund site contaminated with a variety of materials, including organochlorine pesticides, metals, and nerve gas production by-products. Radio-collared deer were tracked for 1 to 3 years (1989–1992) to identify relative exposure to contaminants based on telemetry locations plotted on grid maps depicting known soil contaminant concentrations. At the end of the study, all animals were in fair or good body condition at the time of necropsy. Mean ages of mule deer and white-tailed deer were 7.4 (range 4–12) and 10.6 years (range 5–17), respectively. At necropsy, tissues were collected from the deer for serology, histopathology, and analysis for eight chlorinated hydrocarbons and two metals. Detectable residues of mercury were found in the kidneys of 10 deer (range 0.055–0.096 μg/g), dieldrin was found in fat ( n = 9) (range 0.02–0.72 μg/g), liver ( n = 4) (range 0.017–0.12 μg/g), and brain ( n = 1, 0.018 μg/g), and DDE was found in the muscle of one animal (0.02 μg/g). Relative exposure estimates derived from telemetry and soil contamination data were correlated with tissue levels of dieldrin ( p < 0.001) and mercury ( p = 0.05). Two mule deer had severe testicular atrophy, and one of these animals also had antler deformities. The prevalence of antibodies against epizootic hemorrhagic disease serotype 2 was 85%.

Colorado↗

Evaluation of ability of reference toxicity tests to identify stress in laboratory populations of the amphipod Hyalella azteca

Standard methods for conducting toxicity tests imply that the condition of test organisms can be established using reference toxicity tests. However, only a limited number of studies have evaluated whether reference toxicity tests can actually be used to determine if organisms are in good condition at the start of a test. We evaluated the ability of reference toxicants to identify stress associated with starvation in laboratory populations of the amphipod Hyalella azteca using acute toxicity tests and four reference toxicants: KCl, CdCl2, sodium pentachlorophenate (NaPCP), and carbaryl. Stress associated with severe starvation was observed with exposure of amphipods to carbaryl or NaPCP but not with exposure to KCl or CdCl2 (i.e., lower LC50 with severe starvation). Although the LC50s for NaPCP and carbaryl were statistically different between starved and fed amphipods, this difference may not be biologically significant given the variability expected in acute lethality tests. Stress associated with sieving, heat shock, or cold shock of amphipods before the start of a test was not evident with exposure to carbaryl or KCl as reference toxicants. The chemicals evaluated in this study provided minimal information about the condition of the organisms used to start a toxicity test. Laboratories should periodically perform reference toxicity tests to assess the sensitivity of life stages or strains of test organisms. However, use of other test acceptability criteria required in standard methods such as minimum survival, growth, or reproduction of organisms in the control treatment at the end of a test, provides more useful information about the condition of organisms used to start a test compared to data generated from reference toxicity tests.

Environmental Toxicology and Chemistry↗

Evaluating sediment chemistry and toxicity data using logistic regression modeling

This paper describes the use of logistic-regression modeling for evaluating matching sediment chemistry and toxicity data. Contaminant- specific logistic models were used to estimate the percentage of samples expected to be toxic at a given concentration. These models enable users to select the probability of effects of concern corresponding to their specific assessment or management objective or to estimate the probability of observing specific biological effects at any contaminant concentration. The models were developed using a large database (n = 2,524) of matching saltwater sediment chemistry and toxicity data for field-collected samples compiled from a number of different sources and geographic areas. The models for seven chemicals selected as examples showed a wide range in goodness of fit, reflecting high variability in toxicity at low concentrations and limited data on toxicity at higher concentrations for some chemicals. The models for individual test endpoints (e.g., amphipod mortality) provided a better fit to the data than the models based on all endpoints combined. A comparison of the relative sensitivity of two amphipod species to specific contaminants illustrated an important application of the logistic model approach.

Environmental Toxicology and Chemistry↗

The effects of ultraviolet-B radiation on the toxicity of fire-fighting chemicals

The interactive effects of ultraviolet (UV) and fire-retardant chemicals were evaluated by exposing rainbow trout (Oncorhyncus mykiss) juveniles and tadpoles of southern leopard frogs (Rana sphenocephala) to six fire-retardant formulations with and without sodium ferrocyanide (yellow prussiate of soda [YPS]) and to YPS alone under three simulated UV light treatments. Yellow prussiate of soda is used as a corrosion inhibitor in some of the fire-retardant chemical formulations. The underwater UV intensities measured were about 2 to 10% of surface irradiance measured in various aquatic habitats and were within tolerance limits for the species tested. Mortality of trout and tadpoles exposed to Fire-Trol?? GTS-R, Fire-Trol 300-F, Fire-Trol LCA-R, and Fire-Trol LCA-F was significantly increased in the presence of UV radiation when YPS was present in the formulation. The boreal toad (Bufo boreas), listed as endangered by the state of Colorado (USA), and southern leopard frog were similar in their sensitivity to these chemicals. Photoenhancement of fire-retardant chemicals can occur in a range of aquatic habitats and may be of concern even when optical clarity of water is low; however, other habitat characteristics can also reduce fire retardant toxicity.

Environmental Toxicology and Chemistry↗