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Dissolved organic matter reduces algal accumulation of methylmercury

Dissolved organic matter (DOM) significantly decreased accumulation of methylmercury (MeHg) by the diatom Cyclotella meneghiniana in laboratory experiments. Live diatom cells accumulated two to four times more MeHg than dead cells, indicating that accumulation may be partially an energy-requiring process. Methylmercury enrichment in diatoms relative to ambient water was measured by a volume concentration factor (VCF). Without added DOM, the maximum VCF was 32 x 10 4 , and the average VCF (from 10 to 72 h) over all experiments was 12.6 x 10 4 . At very low (1.5 mg/L) added DOM, VCFs dropped by approximately half. At very high (20 mg/L) added DOM, VCFs dropped 10-fold. Presumably, MeHg was bound to a variety of reduced sulfur sites on the DOM, making it unavailable for uptake. Diatoms accumulated significantly more MeHg when exposed to transphilic DOM extracts than hydrophobic ones. However, algal lysate, a labile type of DOM created by resuspending a marine diatom in freshwater, behaved similarly to a refractory DOM isolate from San Francisco Bay. Addition of 67 μM L-cysteine resulted in the largest drop in VCFs, to 0.28 x 10 4 . Although the DOM composition influenced the availability of MeHg to some extent, total DOM concentration was the most important factor in determining algal bioaccumulation of MeHg.

Environmental Toxicology and Chemistry↗

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↗

Adult tree swallow survival on the polychlorinated biphenyl-contaminated Hudson River, New York, USA, between 2006 and 2010

The upper Hudson River basin in east central New York, USA, is highly contaminated, primarily with polychlorinated biphenyls (PCBs). Reduced adult survival has been documented in tree swallows ( Tachycineta bicolor ) at a similarly PCB-contaminated river system in western Massachusetts. The purpose of the present study was to assess whether adult survival of tree swallows was likewise affected in the Hudson River basin. Between 2006 and 2010, a total of 521 female tree swallows were banded, of which 148 were retrapped at least once. The authors used Program MARK and an information theoretic approach to test the hypothesis that PCB contamination reduced annual survival of female tree swallows. The model that best described the processes that generated the capture history data included covariate effects of year and female plumage coloration on survival but not PCB/river. Annual survival rates of brown-plumaged females (mostly one year old) were generally lower (mean phi = 0.39) than those of blue-plumaged females (mean phi = 0.50, one year or older). Poor early spring weather in 2007 was associated with reduced survival in both plumage-color groups compared to later years. Models with the effects of PCB exposure on survival (all ΔAICc values >5.0) received little support.

New York↗

The relationship between total cholinesterase activity and mortality in four butterfly species

The relationship between total cholinesterase activity (TChE) and mortality in four butterfly species (great southern white [ Ascia monuste ], common buckeye [ Junonia coenia ], painted lady [ Vanessa cardui ], and julia butterflies [ Dryas julia ]) was investigated. Acute contact toxicity studies were conducted to evaluate the response (median lethal dose [LD50] and TChE) of the four species following exposure to the organophosphate insecticide naled. The LD50 for these butterflies ranged from 2.3 to 7.6 μg/g. The average level of TChE inhibition associated with significant mortality ranged from 26 to 67%, depending on the species. The lower bounds of normal TChE activity (2 standard deviations less than the average TChE for reference butterflies) ranged from 8.4 to 12.3 μM/min/g. As a percentage of the average reference TChE activity for the respective species, the lower bounds were similar to the inhibition levels associated with significant mortality, indicating there was little difference between the dose resulting in significant TChE inhibition and that resulting in mortality.

Environmental Toxicology and Chemistry↗

Productivity, embryo and eggshell characteristics, and contaminants in bald eagles from the Great Lakes, USA, 1986 to 2000

Chlorinated hydrocarbon concentrations in eggs of fish-eating birds from contaminated environments such as the Great Lakes of North America tend to be highly intercorrelated, making it difficult to elucidate mechanisms causing reproductive impairment, and to ascribe cause to specific chemicals. An information- theoretic approach was used on data from 197 salvaged bald eagle ( Haliaeetus leucocephalus ) eggs (159 clutches) that failed to hatch in Michigan and Ohio, USA (1986–2000). Contaminant levels declined over time while eggshell thickness increased, and by 2000 was at pre-1946 levels. The number of occupied territories and productivity increased during 1981 to 2004. For both the entire dataset and a subset of nests along the Great Lakes shoreline, polychlorinated biphenyls (ΣPCBs, fresh wet wt) were generally included in the most parsimonious models (lowest-Akaike's information criterion [AICs]) describing productivity, with significant declines in productivity observed above 26 µg/g ΣPCBs (fresh wet wt). Of 73 eggs with a visible embryo, eight (11%) were abnormal, including three with skewed bills, but they were not associated with known teratogens, including ΣPCBs. Eggs with visible embryos had greater concentrations of all measured contaminants than eggs without visible embryos; the most parsimonious models describing the presence of visible embryos incorporated dieldrin equivalents and dichlorodiphenyldichloroethylene (DDE). There were significant negative correlations between eggshell thickness and all contaminants, with ΣPCBs included in the most parsimonious models. There were, however, no relationships between productivity and eggshell thickness or Ratcliffe's index. The ΣPCBs and DDE were negatively associated with nest success of bald eagles in the Great Lakes watersheds, but the mechanism does not appear to be via shell quality effects, at least at current contaminant levels, while it is not clear what other mechanisms were involved.

Great Lakes↗

Chlorophacinone residues in mammalian prey at a black-tailed prairie dog colony

Black-tailed prairie dogs (BTPDs), Cynomys ludovicianus, are an important prey for raptors; therefore, the use of the rodenticide Rozol (0.005% chlorophacinone active ingredient) to control BTPDs raises concern for secondary poisonings resulting from the consumption of contaminated prey by raptors. In the present study, the authors observed Rozol exposure and adverse effects to mammalian prey on 11 of 12 search days of the study. Mammalian hepatic chlorophacinone residues ranged from 0.44 to 7.56 µg/g. Poisoned prey availability was greater than previously reported.

Environmental Toxicology and Chemistry↗

Species-specific and transgenerational responses to increasing salinity in sympatric freshwater gastropods

Freshwater salinization is a global concern partly attributable to anthropogenic salt contamination. The authors examined the effects of increased salinity (as NaCl, 250-4,000 µS/cm, specific conductance) on two sympatric freshwater gastropods ( Helisoma trivolvis and Physa pomillia ). Life stage sensitivities were determined by exposing naive eggs or naive juveniles (through adulthood and reproduction). Additionally, progeny eggs from the juvenile-adult exposures were maintained at their respective parental salinities to examine transgenerational effects. Naive H. trivolvis eggs experienced delayed development at specific conductance > 250 µS/cm; reduced survivorship and reproduction were also seen in juvenile H. trivolvis at 4,000 µS/cm. Survival and growth of P. pomilia were not affected by increased salinity following egg or juvenile exposures. Interestingly, the progeny of H. trivolvis exposed to higher salinity may have gained tolerance to increased salinity whereas P. pomilia progeny may have experienced negative transgenerational effects. The present study demonstrates that freshwater snail species vary in their tolerance to salinization and also highlights the importance of multigenerational studies, as stressor impacts may not be readily apparent from shorter term exposures.

Environmental Toxicology and Chemistry↗

Gene expression, glutathione status and indicators of hepatic oxidative stress in laughing gull (Larus atricilla) hatchlings exposed to methylmercury

Despite extensive studies of methylmercury (MeHg) toxicity in birds, molecular effects on birds are poorly characterized. To improve our understanding of toxicity pathways and identify novel indicators of avian exposure to Hg, the authors investigated genomic changes, glutathione status, and oxidative status indicators in liver from laughing gull (Larus atricilla) hatchlings that were exposed in ovo to MeHg (0.05–1.6 µg/g). Genes involved in the transsulfuration pathway, iron transport and storage, thyroid-hormone related processes, and cellular respiration were identified by suppression subtractive hybridization as differentially expressed. Quantitative polymerase chain reaction (qPCR) identified statistically significant effects of Hg on cytochrome C oxidase subunits I and II, transferrin, and methionine adenosyltransferase RNA expression. Glutathione-S-transferase activity and protein-bound sulfhydryl levels decreased, whereas glucose-6-phosphate dehydrogenase activity increased dose-dependently. Total sulfhydryl concentrations were significantly lower at 0.4 µg/g Hg than in controls. T ogether, these endpoints provided some evidence of compensatory effects, but little indication of oxidative damage at the tested doses, and suggest that sequestration of Hg through various pathways may be important for minimizing toxicity in laughing gulls. This is the first study to describe the genomic response of an avian species to Hg. Laughing gulls are among the less sensitive avian species with regard to Hg toxicity, and their ability to prevent hepatic oxidative stress may be important for surviving levels of MeHg exposures at which other species succumb.

Environmental Toxicology and Chemistry↗

Net trophic transfer efficiencies of polychlorinated biphenyl congeners to lake trout ( Salvelinus namaycush ) from its prey

Lake trout ( Salvelinus namaycush ) were fed bloater ( Coregonus hoyi ) in eight laboratory tanks over a 135-d experiment. At the start of the experiment, four to nine fish in each tank were sacrificed, and the concentrations of 75 polychlorinated biphenyl (PCB) congeners within these fish were determined. Polychlorinated biphenyl congener concentrations were also determined in the 10 lake trout remaining in each of the eight tanks at the end of the experiment as well as in the bloater fed to the lake trout. Each lake trout was weighed at the start and the end of the experiment, and the amount of food eaten by the lake trout was recorded. Using these measurements, net trophic transfer efficiency (γ) from the bloater to the lake trout in each of the eight tanks was calculated for each of the 75 congeners. Results showed that γ did not vary significantly with the degree of chlorination of the PCB congeners, and γ averaged 0.66 across all congeners. However,γ did show a slight, but significant, decrease as log KOW increased from 6.0 to 8.2. Activity level of the lake trout did not have a significant effect on γ.

Environmental Toxicology and Chemistry↗

Chronic hydrocarbon exposure of harlequin ducks in areas affected by the Selendang Ayu oil spill at Unalaska Island, Alaska

We evaluated chronic exposure of harlequin ducks (Histrionicus histrionicus) to hydrocarbons associated with the 2004 M/V Selendang Ayu oil spill at Unalaska Island, Alaska. We measured levels of hepatic 7-ethoxyresorufin-O-deethylase activity (EROD) in liver biopsy samples as an indicator of hydrocarbon exposure in three oiled bays and one reference bay in 2005, 2006, and 2008. Median EROD activity in ducks from oiled bays was significantly higher than in the reference bay in seven of nine pairwise comparisons. These results indicated that harlequin ducks were exposed to lingering hydrocarbons more than three years after the spill.

Alaska↗

Toxicity of sediments potentially contaminated by coal mining and natural gas extraction to unionid mussels and commonly tested benthic invertebrates

Sediment toxicity tests were conducted to assess potential effects of contaminants associated with coal mining or natural gas extraction activities in the upper Tennessee River basin and eastern Cumberland River basin in the United States. Test species included two unionid mussels (rainbow mussel, Villosa iris , and wavy-rayed lampmussel, Lampsilis fasciola , 28-d exposures), and the commonly tested amphipod, Hyalella azteca (28-d exposure) and midge, Chironomus dilutus (10-d exposure). Sediments were collected from seven test sites with mussel communities classified as impacted and in proximity to coal mining or gas extraction activities, and from five reference sites with mussel communities classified as not impacted and no or limited coal mining or gas extraction activities. Additional samples were collected from six test sites potentially with high concentrations of polycyclic aromatic hydrocarbons (PAHs) and from a test site contaminated by a coal ash spill. Mean survival, length, or biomass of one or more test species was reduced in 10 of 14 test samples (71%) from impacted areas relative to the response of organisms in the five reference samples. A higher proportion of samples was classified as toxic to mussels (63% for rainbow mussels, 50% for wavy-rayed lampmussels) compared with amphipods (38%) or midge (38%). Concentrations of total recoverable metals and total PAHs in sediments did not exceed effects-based probable effect concentrations (PECs). However, the survival, length, or biomasses of the mussels were reduced significantly with increasing PEC quotients for metals and for total PAHs, or with increasing sum equilibrium-partitioning sediment benchmark toxic units for PAHs. The growth of the rainbow mussel also significantly decreased with increasing concentrations of a major anion (chloride) and major cations (calcium and magnesium) in sediment pore water. Results of the present study indicated that (1) the findings from laboratory tests were generally consistent with the field observations of impacts on mussel populations; (2) total recoverable metals, PAHs, or major ions, or all three in sediments might have contributed to the sediment toxicity; (3) the mussels were more sensitive to the contaminants in sediments than the commonly tested amphipod and midge; and (4) a sediment toxicity benchmark of 1.0 based on PECs may not be protective of mussels.

Environmental Toxicology and Chemistry↗

Effects of the herbicide imazapyr on juvenile Oregon spotted frogs

Conflict between native amphibians and aquatic weed management in the Pacific Northwest is rarely recognized because most native stillwater-breeding amphibian species move upland during summer, when herbicide application to control weeds in aquatic habitats typically occurs. However, aquatic weed management may pose a risk for aquatic species present in wetlands through the summer, such as the Oregon spotted frog (OSF, Rana pretiosa), a state endangered species in Washington. Acute toxicity of herbicides used to control aquatic weeds tends to be low, but the direct effects of herbicide tank mixes on OSFs have remained unexamined. We exposed juvenile OSFs to tank mixes of the herbicide imazapyr, a surfactant, and a marker dye in a 96-h static-renewal test. The tank mix was chosen because of its low toxicity to fish and its effectiveness in aquatic weed control. Concentrations were those associated with low-volume (3.5 L/ha) and high-volume (7.0 L/ha) applications of imazapyr and a clean-water control. Following exposure, frogs were reared for two months in clean water to identify potential latent effects on growth. Endpoints evaluated included feeding behavior, growth, and body and liver condition indices. We recorded no mortalities and found no significant differences for any end point between the herbicide-exposed and clean-water control frogs. The results suggest that imazapyr use in wetland restoration poses a low risk of direct toxic effects on juvenile OSFs.

Oregon↗

Embryo malposition as a potential mechanism for mercury-induced hatching failure in bird eggs

We examined the prevalence of embryo malpositions and deformities in relation to total mercury (THg) and selenium (Se) concentrations in American avocet ( Recurvirostra americana ), black‐necked stilt ( Himantopus mexicanus ), and Forster's tern ( Sterna forsteri ) eggs in San Francisco Bay (CA, USA) during 2005 to 2007. Overall, 11% of embryos were malpositioned in eggs ≥18 d of age ( n = 282) and 2% of embryos were deformed in eggs ≥13 d of age ( n = 470). Considering only those eggs that failed to hatch ( n = 62), malpositions occurred in 24% of eggs ≥18 d of age and deformities occurred in 7% of eggs ≥13 d of age. The probability of an embryo being malpositioned increased with egg THg concentrations in Forster's terns, but not in avocets or stilts. The probability of embryo deformity was not related to egg THg concentrations in any species. Using a reduced dataset with both Se and THg concentrations measured in eggs ( n = 87), we found no interaction between Se and THg on the probability of an embryo being malpositioned or deformed. Results of the present study indicate that embryo malpositions were prevalent in waterbird eggs that failed to hatch and the likelihood of an embryo being malpositioned increased with egg THg concentrations in Forster's terns. We hypothesize that malpositioning of avian embryos may be one reason for mercury‐related hatching failure that occurs late in incubation, but further research is needed to elucidate this potential mechanism.

Environmental Toxicology and Chemistry↗

Immunological and reproductive health assessment in herring gulls and black-crowned night herons in the Hudson–Raritan Estuary

Previous studies have shown inexplicable declines in breeding waterbirds within western New York/New Jersey Harbor between 1996 and 2002 and elevated polychlorinated dibenzo- p -dioxins and polychlorinated biphenyls (PCBs) in double-crested cormorant ( Phalacrocorax auritus ) eggs. The present study assessed associations between immune function, prefledgling survival, and selected organochlorine compounds and metals in herring gulls ( Larus argentatus ) and black-crowned night herons ( Nycticorax nycticorax ) in lower New York Harbor during 2003. In pipping gull embryos, lymphoid cells were counted in the thymus and bursa of Fabricius (sites of T and B lymphocyte maturation, respectively). The phytohemagglutinin (PHA) skin response assessed T cell function in gull and heron chicks. Lymphocyte proliferation was measured in vitro in adult and prefledgling gulls. Reference data came from the Great Lakes and Bay of Fundy. Survival of prefledgling gulls was poor, with only 0.68 and 0.5 chicks per nest surviving to three and four weeks after hatch, respectively. Developing lymphoid cells were reduced 51% in the thymus and 42% in the bursa of gull embryos from New York Harbor. In vitro lymphocyte assays demonstrated reduced spontaneous proliferation, reduced T cell mitogen-induced proliferation, and increased B cell mitogen-induced proliferation in gull chicks from New York Harbor. The PHA skin response was suppressed 70 to 80% in gull and heron chicks. Strong negative correlations ( r = –0.95 to –0.98) between the PHA response and dioxins and PCBs in gull livers was strong evidence suggesting that these chemicals contribute significantly to immunosuppression in New York Harbor waterbirds.

New Jersey, New York↗

Assessing ongoing sources of dissolved-phase polychlorinated biphenyls in a contaminated stream

Few studies assess the potential of ongoing sources of “fresh” polychlorinated biphenyls (PCBs) to aquatic systems when direct discharge to the environment has been eliminated. In the present study, the authors used single-layered, low-density polyethylene samplers (PEs) to measure total PCB concentrations, congener profiles, and enantiomeric fractions (EFs) in a contaminated stream and to provide multiple lines of evidence for assessing ongoing inputs of PCB. Concentrations were well above background levels that have been monitored for years. Concentrations significantly increased with distance, the farthest downstream PE concentrations being almost five times greater than those at 79 m downstream of a historical point source. The PCBs in the PEs at 79 m downstream of the contamination source were dominated by low K OW congeners, similar to those in the mixture of Aroclors 1016 and 1254 (4:1 v/v) historically released from the former capacitor manufacturer. The only two chiral congeners detected in the PEs downstream were PCBs 91 and 95. The EF values were nonracemic for PCB 91, while the values were either racemic or near racemic for PCB 95. Increased PCB concentrations with distance and a congener composition of predominantly low-weight congeners in the PEs at 79 m downstream of the plant site suggested an ongoing PCB source from the plant site. Chiral signatures suggested aerobic biotransformation of dissolved PCBs but did not shed any light on possible ongoing PCB inputs.

Environmental Toxicology and Chemistry↗

Ecotoxicology of organochlorine chemicals in birds of the Great Lakes

Silent Spring was fulfilled in the United States with passage of environmental legislation such as the Clean Water Act, the Federal Insecticide, Fungicide, and Rodenticide Act, and the Toxic Substance Control Act in the 1970s. Carson's writings, television interviews, and testimony before Congress alerted a nation and the world to the unintended effects of persistent, bioaccumulative chemicals on populations of fish, wildlife, and possibly humans. Her writings in the popular press brought attention to scientific findings that declines in populations of a variety of birds were directly linked to the widespread use of dichlorodiphenyltrichloroethane (DDT) in agriculture, public health, and horticulture. By the 1970s, DDT and other persistent organic pollutants (POPs) were being banned or phased out, and the intent of these regulatory acts became apparent in a number of locations across the United States, including the Great Lakes. Concentrations of DDT and its major product of transformation, dichlorodiphenylchloroethane (DDE), were decreasing in top predators, such as bald eagles (Haliaeetus leucocephalus), osprey (Pandion haliaetus), colonial waterbirds, and other fish-eating wildlife. Eggshell thinning and the associated mortality of bird embryos caused by DDE had decreased in the Great Lakes and elsewhere by the early 1980s.

Environmental Toxicology and Chemistry↗

Perfluorinated compound concentrations in great blue heron eggs near St. Paul, Minnesota, USA, in 1993 and 2010-2011

A great blue heron (Ardea herodias) colony on Pig's Eye Island on the Mississippi River near St. Paul, Minnesota, USA, is located near several potential perfluorinated compound (PFC) sources. The PFC concentrations in great blue heron eggs reported from a 1993 collection from the Pig's Eye colony were among the highest measured in bird eggs worldwide. The objective of this investigation was to determine whether PFC concentrations in great blue heron eggs at the Pig's Eye colony have changed since 1993. Total PFC concentrations in great blue heron eggs collected at the Pig's Eye colony in 2010 and 2011 (geometric mean = 340 and 492 ng/g wet wt) were 60% lower than the 1993 collection (1,015 ng/g wet wt). Among PFCs, perfluoroalkyl sulfonate concentrations were lower and perfluoroalkyl carboxylate concentrations were higher in the 2010 and 2011 collections. Two of 20 (10%) of the eggs analyzed from Pig's Eye in 2010 and 2011 were >1,000 ng PFCs/g wet weight and the maximum PFC value (2,506 ng PFCs/g wet wt) measured in 2010 and 2011 was among the highest PFC concentration reported in bird eggs. These high concentrations are at levels associated with physiological and neurological effects in birds.

Minnesota↗

Chronic toxicity of nickel-spiked freshwater sediments: variation in toxicity among eight invertebrate taxa and eight sediments

This study evaluated the chronic toxicity of Ni-spiked freshwater sediments to benthic invertebrates. A 2-step spiking procedure (spiking and sediment dilution) and a 2-stage equilibration period (10 wk anaerobic and 1 wk aerobic) were used to spike 8 freshwater sediments with wide ranges of acid-volatile sulfide (AVS; 0.94–38 µmol/g) and total organic carbon (TOC; 0.42–10%). Chronic sediment toxicity tests were conducted with 8 invertebrates ( Hyalella azteca, Gammarus pseudolimnaeus , Chironomus riparius, Chironomus dilutus , Hexagenia sp., Lumbriculus variegatus, Tubifex tubifex , and Lampsilis siliquoidea ) in 2 spiked sediments. Nickel toxicity thresholds estimated from species-sensitivity distributions were 97 µg/g and 752 µg/g (total recoverable Ni; dry wt basis) for sediments with low and high concentrations of AVS and TOC, respectively. Sensitive species were tested with 6 additional sediments. The 20% effect concentrations (EC20s) for Hyalella and Gammarus , but not Hexagenia , were consistent with US Environmental Protection Agency benchmarks based on Ni in porewater and in simultaneously extracted metals (SEM) normalized to AVS and TOC. For Hexagenia , sediment EC20s increased at less than an equimolar basis with increased AVS, and toxicity occurred in several sediments with Ni concentrations in SEM less than AVS. The authors hypothesize that circulation of oxygenated water by Hexagenia led to oxidation of AVS in burrows, creating microenvironments with high Ni exposure. Despite these unexpected results, a strong relationship between Hexagenia EC20s and AVS could provide a basis for conservative site-specific sediment quality guidelines for Ni.

Environmental Toxicology and Chemistry↗