The bioaccumulation of persistent contaminants by zebra mussels and their effects on state-endangered common terns

Common terns currently are listed as endangered or threatened in many states, including Illinois, Vermont, Pennsylvania, Ohio, Wisconsin, Michigan, and New York, and a species of special concern by the U.S. Fish and Wildlife Service (USFWS, 2002). The sole remaining nesting colony in Illinois is located at the Naval Station Great Lakes (NSGL) in Lake County where intensive management by the Illinois Department of Natural Resources has reduced nest predation and increased the number of eggs that hatch. However, the overall reproductive success (the number of young successfully reaching independence) has not improved. Observations of gross deformities in hatchlings (i.e. compromised feather development and cross-bill), lethargic behavior of young birds, and lesions, suggested the influence of environmental contaminants (Jablonski et al., 2005). I investigated if there were significant levels of environmental contaminants in eggs and nestlings of common terns. While there were minimal concentration of selenium, mercury, lead, and cadmium, there were large concentration of polychlorinated biphenyls (PCBs) in both the eggs and nestlings. The greater amounts of PCBs in older chicks than younger chicks suggest local contamination. In order to potentially manage the factors responsible for exposing the terns to PCBs I investigated the pathway by which PCBs were exposed to terns. The two most likely biological pathways as determined by research on Great Lake fishes were investigated. The first pathway is through atmospheric deposition of PCBs and resuspension of PCB-ladel sediment which are subsequently acquired by filter-feeding fish (e.g. alewives, Alosa pseudoharengus) and then pelagic fish (e.g. lake trout, Salvelinus namaychus) or in this case terns. The second pathway explored was via the biodeposits of zebra mussels which are consumed by round gobies (Neogobius melanostromus) and ultimately littoral fish (e.g. small-mouthed bass, Micropterus dolomieui) or terns. Because common terns breed in near-shore sites where concentrations of zebra mussels are found, as well as forage in more pelagic environments it is possible that either or both pathways may be contributing to their PCB exposure. Field experiments and stable isotope analyses demonstrated that the most likely pathway by which terns are exposed to PCBs is via alewives, similar to how apex predators such as lake trout acquire PCBs. Biodeposits from zebra mussels do not appear to be a significant factor in PCB accumulation in terns. The impact of PCB exposure on birds can vary widely, however in this situation we choise to investigate one specific behavior often affected by PCB exposure, parental attentiveness. PCBs are known to cause endocrine disruption which ultimately results in reduced brooding of young and incubation of eggs. I used temperature sensors to quantify nest temperatures and parental attentiveness during incubation. High concentrations of PCBs in our study population appear to be leading to poor parental attentiveness, and extended periods of absence during incubation and brooding, ultimately leading to poor reproductive success. Common terns are perilously close to being extirpated in Illinois and management of PCB exposure will be difficult. I propose that additional testing should be conducted to locate a site with less PCB contamination and then to move the tern colony to this location, possibly using social cues as has been done with other tern species in Illinois. PCBs are having a profound impact on common tern populations in Illinois and without moving the colony it is likely that the population will continue to decline.

BALD EAGLES (HALIAEETUS LEUCOCEPHALUS) AS INDICATORS OF GREAT LAKES ECOSYSTEM HEALTH

Environmental indicators have been proposed as a means to assess ecological integrity, monitoring both chemical and biological stressors. In this study, we used nestling bald eagles as indicators to quantify direct or indirect tertiary-level contaminant exposure. The spatial and temporal trends of polychlorinated biphenyl (PCB) congeners were evaluated in nestling plasma from 1999–2014. Two hexa-chlorinated congeners, PCB-138 and 153, were detected with the highest frequency and greatest concentrations throughout Michigan. Less-chlorinated congeners such as PCB-52 and 66 however, comprised a greater percentage of total PCB concentrations in nestlings proximate to urbanized areas, such as along the shorelines of Lake Erie. Toxic equivalents were greatest in the samples collected from nestlings located on Lake Erie, followed by the other Great Lakes spatial regions. Nestling plasma samples were also used to measure concentrations of the most heavily-used group of flame retardants, brominated diphenyl ethers (BDEs), and three groups of alternative flame retardants, non-BDE Brominated Flame Retardants (NBFRS), Dechloranes, and organophosphate esters (OPs). BDE-47, 99 and 100 contributed the greatest to total BDE concentrations. Concentrations of structurally similar NBFRs found in this study and recent atmospheric studies indicate that they are largely used as replacements to previously used BDE mixtures. A variety of Dechloranes, or derivatives of Mirex and Dechlorane Plus, were measured. Although, measured at lesser concentrations, environmental behavior of these compounds may be similar to mirex and warrant future research in aquatic species. Concentrations of OPs in nestling plasma were two to three orders of magnitude greater than all other groups of flame retardants. In addition to chemical indicators, bald eagles have also been proposed as indicators to identify ecological stressors using population measures that are tied to the fitness of individuals and populations. Using mortality as a population vitality rate, vehicle collisions were found to be the main source of mortality with a greater incidence for females during white-tailed deer (Odocoileus virginianus) hunting months and spring snow-melt. Lead poisoning was the second greatest source of mortality, with sources likely due to unretrieved hunter-killed, white-tailed deer carcasses, and possibly exacerbated by density-dependent effects due to the growing population in Michigan.

Development of measurement and modeling techniques to quantify atmospheric deposition of persistent, bioaccumulative and toxic chemicals in the Great Lakes

Measurement and modeling techniques were developed to improve over-water gaseous air-water exchange measurements for persistent bioaccumulative and toxic chemicals (PBTs). Analytical methods were applied to atmospheric measurements of hexachlorobenzene (HCB), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). Additionally, the sampling and analytical methods are well suited to study semivolatile organic compounds (SOCs) in air with applications related to secondary organic aerosol formation, urban, and indoor air quality. A novel gas-phase cleanup method is described for use with thermal desorption methods for analysis of atmospheric SOCs using multicapillary denuders. The cleanup selectively removed hydrogen-bonding chemicals from samples, including much of the background matrix of oxidized organic compounds in ambient air, and thereby improved precision and method detection limits for nonpolar analytes. A model is presented that predicts gas collection efficiency and particle collection artifact for SOCs in multicapillary denuders using polydimethylsiloxane (PDMS) sorbent. An approach is presented to estimate the equilibrium PDMS-gas partition coefficient (Kpdms) from an Abraham solvation parameter model for any SOC. A high flow rate (300 L min-1) multicapillary denuder was designed for measurement of trace atmospheric SOCs. Overall method precision and detection limits were determined using field duplicates and compared to the conventional high-volume sampler method. The high-flow denuder is an alternative to high-volume or passive samplers when separation of gas and particle-associated SOCs upstream of a filter and short sample collection time are advantageous. A Lagrangian internal boundary layer transport exchange (IBLTE) Model is described. The model predicts the near-surface variation in several quantities with fetch in coastal, offshore flow: 1) modification in potential temperature and gas mixing ratio, 2) surface fluxes of sensible heat, water vapor, and trace gases using the NOAA COARE Bulk Algorithm and Gas Transfer Model, 3) vertical gradients in potential temperature and mixing ratio. The model was applied to interpret micrometeorological measurements of air-water exchange flux of HCB and several PCB congeners in Lake Superior. The IBLTE Model can be applied to any scalar, including water vapor, carbon dioxide, dimethyl sulfide, and other scalar quantities of interest with respect to hydrology, climate, and ecosystem science.