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.

Tourism Media Dynamics: Narratives of the Nation-State

With the premise that the tourism promotional video “China, Forever” provides a crucial access to understanding how tourism engages in a wider circle of socio-culture formation, this dissertation research approaches tourism by examining communicative practices initiated by “China, Forever”. In doing so, it seeks to reveal two dialogues – firstly, between the discursive construction of tourism representational language and China’s nation-state ideology; secondly, between interpretations from overseas Chinese audiences and nation-state narratives delivered via the tourism media. In analyzing the first dialogue, this dissertation reveals that the pursuit of collective and monolithic national imagery has caused a representational violence – one that is committed by the nation-state ideology operated through the organization of tourism language. The very representational coercion itself, however, signifies the nature of tourism media as a vehicle mediating the global gaze and China’s self-representation; illuminating the fact that China’s nation-state building is only to be understood as deeply-grounded in the complexity of postcolonial politics. Furthermore, in a dialectic view, such finding consolidates the nature of “China, Forever” as a cultural product that actively exists as a component in the overall social fabric, co-creating a wider circle of culture politics together with other genres of media products; thus, calling for a more comprehensive understanding of tourism media at large. In the second approach, this dissertation seeks to understand how the tourism video “China, Forever” mediates the relationship between tourism narratives of the nation-state and overseas Chinese individuals; thus bridging together tourism media and ongoing life experiences of the audiences chosen. The analysis reveals that audiences’ interpretations heavily concentrate on resisting and fragmenting the hegemonic nation-state language in “China, Forever”. While some interviewees seek to decentralize the nation-state perspective from aspects of aesthetics, representational style, and representational subjects in “China, Forever” by incorporating their individual memories and past experiences, to some others, the over-polished glorification of China in the mediated tourism discourse is only coercive to China’s social realities experienced by the individual interviewees - the disheartening contrasts of poverty and affluence as well as other social inequalities. From the perspective of the audience group, the Chinese scholars and students at the University of Illinois interviewed for this dissertation research constitute a cohort of exiled audiences for the tourism video “China, Forever”. The audiences subject themselves to voluntary interpellation, a process in which they find themselves defending, negotiating, and resisting the nation-state representation of China – even though they are not its intended audience and have had no input into its production. Nevertheless, such process is one of identification, in which viewers articulate a subject position from which to speak of their own experiences, dilemmas and desires. The usefulness of tourism media discourse in mediating the nation-state narratives and the individual experience is amplified.

Investigations into the mechanism of orotidine 5'-monophosphate decarboxylase: Sources of substrate destabilization and transition state stabilization

Orotidine 5′-monophosphate decarboxylase (OMPDC) achieves a rarely paralleled rate acceleration, yet the catalytic basis prompting this enhancement have yet to be fully elucidated. To accomplish decarboxylation, OMPDC must overcome the high energy barrier due to the localized anionic charge of the intermediate. Mechanistic studies employing enzyme mutagenesis and product or intermediate analogues were used to investigate possible transition state stabilization by a carbene resonance structure. Viability of the carbene structure depends upon a key hydrogen bond between O4 of the substrate and the amide backbone of a conserved serine or threonine. Substitution of the conserved residue with Pro resulted in a kcat/KM of 1 M-1s-1; deletion of the FUMP O4 resulted in a product analogue that does not undergo H6 exchange or inhibit decarboxylation. Hence, indirect evidence reveals the O4-backbone interaction plays an important role for binding and catalysis. OMPDC likely has honed multiple mechanisms to attain its remarkable catalysis. The successful crystallizations of OMPDC a decade ago sparked hypotheses that structure and sequence conserved residues induced productive strain on the substrate-enzyme complex. Here, we demonstrate a new source of stress: a hydrophobic pocket adjacent to the OMP carboxylate that exhibits kinetic parameters characteristic of substrate destabilization. Substitution of these residues with hydrophilic side-chains, by providing hydrogen-bonding partners, decreased kcat by 10 to 10^4–fold. The same substitutions display very little change in the rate of product H6 exchange, supporting that this hydrophobic pocket affects the substrate-enzyme complex before the transition state. We also provide evidence that hydrophilic residues can insert water molecules into the pocket with detrimental effects to catalysis.