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A comprehensive assessment of membrane bioreactor contaminant removal efficacy through analytical chemistry, fish exposures, and microbiome characterization

Treated municipal wastewater effluent is an important pathway for Contaminants of Emerging Concern (CEC) to enter aquatic ecosystems. As the aging wastewater infrastructure in many industrialized countries requires upgrades or replacement, assessing new treatment technologies in the context of CEC effects may provide additional support for science-based resource management. Here, we used three lines of evidence, analytical chemistry, fish exposure experiments, and fish and water microbiome analysis, to assess the effectiveness of membrane bioreactor treatment (MBR) to replace traditional activated sludge treatment. To do this, we sampled a municipal wastewater treatment plant with a split wastewater stream, a portion of which was treated with an MBR and another via an oxidation ditch (OXI). The OXI and MBR treatments substantially reduced most measured CECs compared to the primary effluent (PRI). Only pesticides and some pharmaceuticals were recalcitrant to both secondary treatment methods. While ammonia toxicity of PRI prevented its inclusion in fish exposure experiments, exposure of fish with waters from the OXI or MBR treated wastewater produced only subtle biological differences with no adverse apical outcomes. These findings were consistent with low chemically derived exposure: activity ratios for OXI and MBR. Microbiome analysis of fish and wastewater highlighted the significant reduction of microbial abundance and diversity in the MBR treatment compared to all other treatments. The comparable removal efficacy of CECs in MBR makes it an attractive alternative to traditional OXI, especially when MBR may eliminate the need for tertiary treatment for wastewater disinfection.

Environmental Toxicology and Chemistry↗

PCB-induced changes of a benthic community and expected ecosystem recovery following in situ sorbent amendment

The benthic community was analyzed to evaluate pollution-induced changes for the polychlorinated biphenyl (PCB)-contaminated site at Hunters Point (HP) relative to 30 reference sites in San Francisco Bay, California, USA. An analysis based on functional traits of feeding, reproduction, and position in the sediment shows that HP is depauperate in deposit feeders, subsurface carnivores, and species with no protective barrier. Sediment chemistry analysis shows that PCBs are the major risk drivers at HP (1,570 ppb) and that the reference sites contain very low levels of PCB contamination (9 ppb). Different feeding traits support the existence of direct pathways of exposure, which can be mechanistically linked to PCB bioaccumulation by biodynamic modeling. The model shows that the deposit feeder Neanthes arenaceodentata accumulates approximately 20 times more PCBs in its lipids than the facultative deposit feeder Macoma balthica and up to 130 times more than the filter feeder Mytilus edulis . The comparison of different exposure scenarios suggests that PCB tissue concentrations at HP are two orders of magnitude higher than at the reference sites. At full scale, in situ sorbent amendment with activated carbon may reduce PCB bioaccumulation at HP by up to 85 to 90% under favorable field and treatment conditions. The modeling framework further demonstrates that such expected remedial success corresponds to exposure conditions suggested as the cleanup goal for HP. However, concentrations remain slightly higher than at the reference sites. The present study demonstrates how the remedial success of a sorbent amendment, which lowers the PCB availability, can be compared to reference conditions and traditional cleanup goals, which are commonly based on bulk sediment concentrations.

California↗

Declining aluminum toxicity and the role of exposure duration on brook trout mortality in acidified streams of the Adirondack Mountains, New York, USA

Mortality of brook trout Salvelinus fontinalis and water chemistry were characterized in 6 headwater streams in the western Adirondacks of New York during spring 2015, 2016, and 2017 and compared with results from analogous tests done between 1980 and 2003 in many of the same streams, to assess temporal changes in toxicity and inorganic monomeric aluminum (Al i ) concentrations, and the role of Al i exposure duration on brook trout survival. The Al i concentrations of 2 and 4 µmol L –1 corresponded to low‐to‐moderate and high mortality thresholds, but prolonged exposure to ≥1 µmol Al i L –1 also produced mortality. The variability, mean, and highest Al i concentrations in Buck Creek year round, and in several other streams during spring, have decreased significantly over the past 3 decades. Logistic models indicate that Al i surpassed highly toxic concentrations in Buck Creek for 3 to 4 mo annually during 2001 to 2003 and for 2 to 3 wk annually during 2015 to 2017. The loss of extremely high Al i episodes indicates that toxicity has declined markedly between the 1989 to 1990, 2001 to 2003, and 2015 to 2017 test periods, yet Al i concentrations can still cause moderate‐to‐high and complete (100%) mortality. The logistic models illustrate how mortality of brook trout in several Adirondack streams likely decreased in response to the 1990 Amendments to the United States' Clean Air Act (which decreased acidity, Al i concentrations, and duration of toxic episodes) and offer a means to predict how changes in US regulations that limit emissions of NO x and SO x (and N and S deposition loads) could affect fish survival and stream ecosystems in this region and across the Northeast.

New York↗

Mineralogy and environmental geochemistry of historical iron slag, Hopewell Furnace National Historic Site, Pennsylvania, USA

The Hopewell Furnace National Historic Site in southeastern Pennsylvania, which features an Fe smelter that was operational in the 18th and 19th centuries, is dominated by three slag piles. Pile 1 slag, from the Hopewell Furnace, and pile 2 slag, likely from the nearby Cornwall Furnace, were both produced in cold-blast charcoal-fired smelters. In contrast, pile 3 slag was produced in an anthracite furnace. Ore samples from the nearby Jones and Hopewell mines that fed the smelter are mainly magnetite-rich with some sulfides (pyrite, chalcopyrite, sphalerite) and accessory silicates (quartz, garnet, feldspar, and clay minerals). Slag piles 1 and 2 are similar mineralogically containing predominantly skeletal and dendritic aluminian diopside and augite, skeletal forsteritic olivine, glass, rounded blebs of metallic Fe, and exotic quartz. Olivine is a major phase in all samples from pile 2, whereas it occurs in only a few samples from pile 1. Samples of the <2 mm-size fraction of surface composite slag material or crushed slag from at depth in piles 1 and 2 are mineralogically similar to the large surface slag fragments from those piles with the addition of phases such as feldspars, Fe oxides, and clay minerals that are either secondary weathering products or entrained from the underlying bedrock. Pile 3 slag contains mostly skeletal forsteritic olivine and Ti-bearing aluminian diopside, dendritic or fine-grained subhedral melilite, glass, euhedral spinel, metallic Fe, alabandite–oldhamite solid solution, as well as a sparse Ti carbonitride phase. The bulk chemistry of the slag is dominated by Al 2 O 3 (8.5–16.2 wt.%), CaO (8.2–26.2 wt.%), MgO (4.2–24.7 wt.%), and SiO 2 (36.4–59.8 wt.%), constituting between 81% and 97% of the mass of the samples. Piles 1 and 2 are chemically similar; pile 1 slag overall contains the highest Fe 2 O 3 , K 2 O and MnO, and the lowest MgO concentrations. Pile 3 slag is high in Al 2 O 3 , CaO and S, and low in Fe 2 O 3 , K 2 O and SiO 2 compared to the other piles. In general, piles 1 and 2 are chemically similar to each other, whereas pile 3 is distinct – a conclusion that reflects their mineralogy. The similarities and differences among piles in terms of mineralogy and major element chemistry result from the different smelting conditions under which the slag formed and include the fuel source, the composition of the ore and flux, the type of blast (cold versus hot), which affects the furnace temperature, and other beneficiation methods. The three distinct slag piles at Hopewell are enriched in numerous trace elements, such as As (up to 12 mg/kg), Cd (up to 0.4 mg/kg), Co (up to 31.8 mg/kg), Cu (up to 647 mg/kg), Mn (up to 0.69 wt.%), Pb (up to 172 mg/kg) and Zn (up to 393 mg/kg), together with Fe (13.9 wt.%), when compared to the average for the continental crust, with the <2 mm-size fraction commonly containing the highest concentrations. Enrichments in various elements (e.g., Cd, Co, Cu, Pb, Zn) were also found in the ore samples. Despite these enrichments, comparison of bulk chemistry trace-element concentrations to the environmental guidelines suggests most elements are likely not problematic with the exception of As, Co, Fe and Mn. Leachate tests that simulate weathering indicate Fe (up to 973 μg/L) and Mn (up to 133 μg/L) are readily released in potentially harmful concentrations compared to secondary drinking water and some aquatic ecosystem toxicity criteria. Aluminum and Cu, although not high in the solid compared to environmental guidelines, also exceed relevant criteria in leachate extracts with maximum concentrations of 2700 μg/L and 17.7 μg/L, respectively. In contrast, As and Co, which are significant in the solids, are not leached in concentrations that exceed guidelines (i.e., 3 μg/L or less for both elements). The weathering rates of the Fe metal and Fe oxides, which host Cu and some Fe, are likely higher than the silicate glass, which hosts the majority of Al, Mn and some Fe, and the crystalline silicates and spinels affecting which elements and how much are released into the environment and surrounding aquatic ecosystem. The mineral assemblages and their chemical composition, the bulk sample chemistry, and leachability of trace elements are all important components in understanding the potential environmental impacts of the slag piles.

Pennsylvania↗

Pyrethroid insecticide concentrations and toxicity in streambed sediments and loads in surface waters of the San Joaquin Valley, California, USA

Pyrethroid insecticide use in California, USA, is growing, and there is a need to understand the fate of these compounds in the environment. Concentrations and toxicity were assessed in streambed sediment of the San Joaquin Valley of California, one of the most productive agricultural regions of the United States. Concentrations were also measured in the suspended sediment associated with irrigation or storm‐water runoff, and mass loads during storms were calculated. Western valley streambed sediments were frequently toxic to the amphipod, Hyalella azteca , with most of the toxicity attributable to bifenthrin and cyhalothrin. Up to 100% mortality was observed in some locations with concentrations of some pyrethroids up to 20 ng/g. The western San Joaquin Valley streams are mostly small watersheds with clay soils, and sediment‐laden irrigation runoff transports pyrethroid insecticides throughout the growing season. In contrast, eastern tributaries and the San Joaquin River had low bed sediment concentrations (<1 ng/g) and little or no toxicity because of the preponderance of sandy soils and sediments. Bifenthrin, cyhalothrin, and permethrin were the most frequently detected pyrethroids in irrigation and storm water runoff. Esfenvalerate, fenpropathrin, and resmethrin were also detected. All sampled streams contributed to the insecticide load of the San Joaquin River during storms, but some compounds detected in the smaller creeks were not detected in the San Joaquin River. The two smallest streams, Ingram and Hospital Creeks, which had high sediment toxicity during the irrigation season, accounted for less than 5% of the total discharge of the San Joaquin River during storm conditions, and as a result their contribution to the pyrethroid mass load of the larger river was minimal.

California↗

Intraperitoneal injections as a possible means of generating varied levels of methylmercury in the eggs of birds in field studies

The ideal study of the effects of methylmercury on the reproductive success of a species of bird would be one in which eggs contained mercury concentrations ranging from controls to very heavily contaminated, all at the same site. Such a study cannot be realized at a mercury contaminated area or under laboratory conditions, but could be achieved by introducing methylmercury into breeding females and allowing them to deposit mercury in their eggs. Female mallards (Anas platyrhynchos) were intraperitoneally injected with solutions of methylmercury chloride dissolved in corn oil, propylene glycol, dimethyl sulfoxide, mineral oil, Olestra, Crisco, lard, hard paraffin, and a combination of hard and soft paraffin. In some cases, egg laying was delayed, either due to the solvent itself (in the case of Olestra, Crisco, and lard) or to the highest concentration of methylmercury chloride (500 &mu;g/g) in some of the solvents. Mercury in eggs ranged from a control level (< 0.1 &mu;g/g) to approximately 14 &mu;g/g on a wet weight basis, which more than covers the range of concentrations reported in wild bird eggs. Mercury concentrations in a series of eggs from the same female declined mostly due to excretion of mercury in prior eggs and not because of the length of time since the injection. Intraperitoneal injections hold promise in field studies where one would like to study the reproductive effects of a wide range of methylmercury levels in the eggs of a wild bird and under the natural conditions that exist in the field.

Environmental Toxicology and Chemistry↗

Cytochrome P4501A biomarker indication of oil exposure in harlequin ducks up to 20 years after the Exxon Valdez oil spill

Hydrocarbon-inducible cytochrome P4501A (CYP1A) expression was measured, as ethoxyresorufin- O -deethylase (EROD) activity, in livers of wintering harlequin ducks ( Histrionicus histrionicus ) captured in areas of Prince William Sound, Alaska, USA, oiled by the 1989 Exxon Valdez spill and in birds from nearby unoiled areas, during 2005 to 2009 (up to 20 years following the spill). The present work repeated studies conducted in 1998 that demonstrated that in harlequin ducks using areas that received Exxon Valdez oil, EROD activity was elevated nearly a decade after the spill. The present findings strongly supported the conclusion that average levels of hepatic EROD activity were higher in ducks from oiled areas than those from unoiled areas during 2005 to 2009. This result was consistent across four sampling periods; furthermore, results generated from two independent laboratories using paired liver samples from one of the sampling periods were similar. The EROD activity did not vary in relation to age, sex, or body mass of individuals, nor did it vary strongly by season in birds collected early and late in the winter of 2006 to 2007, indicating that these factors did not confound inferences about observed differences between oiled and unoiled areas. We interpret these results to indicate that harlequin ducks continued to be exposed to residual Exxon Valdez oil up to 20 years after the original spill. This adds to a growing body of literature suggesting that oil spills have the potential to affect wildlife for much longer time frames than previously assumed.

Alaska↗

Interactions between methylmercury and selenomethionine injected into mallard eggs

Methylmercury chloride and seleno-L-methionine were injected separately or in combinations into mallard eggs (Anas platyrhynchos), and embryo mortality and teratogenic effects (deformities) were modeled using a logistic regression model. Methylmercury was injected at doses that resulted in concentrations of 0, 0.2, 0.4, 0.8, and 1.6 µg/g Hg in the egg on a wet weight basis and selenomethionine at doses that resulted in concentrations of 0, 0.1, 0.2, 0.4, and 0.6 µg/g Se in the egg, also on a wet weight basis. When selenomethionine and methylmercury were injected separately, hatching probability decreased in both cases. However, when methylmercury was injected at 1.6 µg/g in combination with selenomethionine at 0.2 µg/g, the presence of the methylmercury resulted in less embryo mortality than had been seen with 0.2 µg/g Se by itself, but it increased the number of deformed embryos and hatchlings. Selenomethionine appeared to be more embryotoxic than equivalent doses of methylmercury when injected into eggs, and both injected methylmercury and selenomethionine were more toxic to mallard embryos than when deposited naturally in the egg by the mother. The underlying mechanisms behind the interactions between methylmercury and selenomethionine and why methylmercury appeared to improve hatching probability of Se-dosed eggs yet increased deformities when the two compounds were combined are unclear. These findings warrant further studies to understand these mechanisms in both laboratory and field settings.

Environmental Toxicology and Chemistry↗

Deposition and accumulation of airborne organic contaminants in Yosemite National Park, Calfornia

Deposition and accumulation of airborne organic contaminants in Yosemite National Park were examined by sampling atmospheric deposition, lichen, zooplankton, and lake sediment at different elevations. Passive samplers were deployed in high‐elevation lakes to estimate surface‐water concentrations. Detected compounds included current‐use pesticides chlorpyrifos, dacthal, and endosulfans and legacy compounds chlordane, dichlorodiphenyltrichloroethane‐related compounds, dieldrin, hexachlorobenzene, and polychlorinated biphenyls. Concentrations in snow were similar among sites and showed little variation with elevation. Endosulfan concentrations in summer rain appeared to coincide with application rates in the San Joaquin Valley. More than 70% of annual pesticide inputs from atmospheric deposition occurred during the winter, largely because most precipitation falls as snow. Endosulfan and chlordane concentrations in lichen increased with elevation, indicating that mountain cold‐trapping might be an important control on accumulation of these compounds. By contrast, chlorpyrifos concentrations were inversely correlated with elevation, indicating that distance from source areas was the dominant control. Sediment concentrations were inversely correlated with elevation, possibly because of the organic carbon content of sediments but also perhaps the greater mobility of organic contaminants at lower elevations. Surface‐water concentrations inferred from passive samplers were at sub–parts‐per‐trillion concentrations, indicating minimal exposure to aquatic organisms from the water column. Concentrations in sediment generally were low, except for dichlorodiphenyldichloroethane in Tenaya Lake, which exceeded sediment guidelines for protection of benthic organisms.

California↗

Relating the ability of mallards to ingest high levels of sediment to potential contaminant exposure in waterfowl

When waterfowl feed from the bottom of bodies of water, they sometimes ingest sediments along with their food, and this sediment can be a major source of contaminants. Learning how much sediment waterfowl can consume in their diet and still maintain their health would be helpful in assessing potential threats from contaminants in sediment. In a controlled laboratory study the maximum tolerated percentage of sediment in the diet of mallards ( Anas platyrhynchos ) was measured. When fed a well‐balanced commercial avian diet, 50, 60, or 70% sediment in the diet on a dry‐weight basis did not cause weight loss over a two‐week period. Ducks fed this same commercial diet, but containing 80 or 90% sediment, lost 8.6 and 15.6% of their body weight, respectively, in the first week on those diets. After factoring in the ability of the mallards to sieve out some of the sediment from their diet before swallowing it, we concluded that the mallards could maintain their health even when approximately half of what they swallowed, on a dry‐weight basis, was sediment.

Environmental Toxicology and Chemistry↗

Risk assessment for adult butterflies exposed to the mosquito control pesticide naled

A prospective risk assessment was conducted for adult butterflies potentially exposed to the mosquito control insecticide naled. Published acute mortality data, exposure data collected during field studies, and morphometric data (total surface area and fresh body weight) for adult butterflies were combined in a probabilistic estimate of the likelihood that adult butterfly exposure to naled following aerial applications would exceed levels associated with acute mortality. Adult butterfly exposure was estimated based on the product of (1) naled residues on samplers and (2) an exposure metric that normalized total surface area for adult butterflies to their fresh weight. The likelihood that the 10th percentile refined effect estimate for adult butterflies exposed to naled would be exceeded following aerial naled applications was 67 to 80%. The greatest risk would be for butterflies in the family Lycaenidae, and the lowest risk would be for those in the family Hesperidae, assuming equivalent sensitivity to naled. A range of potential guideline naled deposition levels is presented that, if not exceeded, would reduce the risk of adult butterfly mortality. The results for this risk assessment were compared with other risk estimates for butterflies, and the implications for adult butterflies in areas targeted by aerial naled applications are discussed.

Environmental Toxicology and Chemistry↗

Acute toxicity of cadmium, lead, zinc, and their mixtures to stream-resident fish and invertebrates

The authors conducted 150 tests of the acute toxicity of resident fish and invertebrates to Cd, Pb, and Zn, separately and in mixtures, in waters from the South Fork Coeur d'Alene River watershed, Idaho, USA. Field-collected shorthead sculpin ( Cottus confusus ), westslope cutthroat trout ( Oncorhynchus clarkii lewisi ), two mayflies ( Baetis tricaudatus and Rhithrogena sp.), a stonefly ( Sweltsa sp.), a caddisfly ( Arctopsyche sp.), a snail ( Gyraulus sp.), and hatchery rainbow trout ( Oncorhynchus mykiss ), were tested with all three metals. With Pb, the mayflies ( Drunella sp., Epeorus sp., and Leptophlebiidae), a Simuliidae black fly, a Chironomidae midge, a Tipula sp. crane fly, a Dytiscidae beetle, and another snail ( Physa sp.), were also tested. Adult westslope cutthroat trout were captured to establish a broodstock to provide fry of known ages for testing. With Cd, the range of 96-h median effect concentrations (EC50s) was 0.4 to >5,329&mu;g/L, and the relative resistances of taxa were westslope cutthroat trout ≈ rainbow trout ≈ sculpin << other taxa; with Pb, EC50s ranged from 47 to 3,323&mu;g/L, with westslope cutthroat trout < rainbow trout < other taxa; and with Zn, EC50s ranged from 21 to 3,704&mu;g/L, with rainbow trout < westslope cutthroat trout ≈ sculpin << other taxa. With swim-up trout fry, a pattern of decreasing resistance with increasing fish size was observed. In metal mixtures, the toxicities of the three metals were less than additive on a concentration-addition basis.

Idaho↗

Toxicity of elevated partial pressures of carbon dioxide to invasive New Zealand mudsnails

The authors tested the efficacy of elevated partial pressures of CO 2 to kill invasive New Zealand mudsnails. The New Zealand mudsnails were exposed to 100 kPa at three water temperatures, and the survival was modeled versus dose as cumulative &deg;C-h. We estimated an LD50 of 59.4&deg;C-h for adult and juvenile New Zealand mudsnails. The results suggest that CO 2 may be an effective and inexpensive lethal tool to treat substrates, tanks, or materials infested with New Zealand mudsnails.

Environmental Toxicology and Chemistry↗

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 &mu;M 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 &Delta;AICc 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 &mu;g/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 &mu;M/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↗