Coastal plant growth and CO2 enrichment: Can the productivity of black needle rush keep pace with sea level rise?

The rate of sea level change has varied considerably over geological time, with rapid increases (0.25 cm yr-1) at the end of the last ice age to more modest increases over the last 4,000 years (0.04 cm yr-1; Hendry 1993). Due to anthropogenic contributions to climate change, however, the rate of sea level rise is expected to increase between 0.10 and 0.25 cm year-1 for many coastal areas (Warrick et al. 1996). Notwithstanding, it has been predicted that over the next 100 years, sea levels along the northeastern coast of North Carolina may increase by an astonishing 0.8 m (0.8 cm yr-1); through a combination of sea-level rise and coastal subsidence (Titus and Richman 2001; Parham et al. 2006). As North Carolina ranks third in the United States with land at or just above sea level, any additional sea rise may promote further deterioration of vital coastal wetland systems. (PDF contains 4 pages)

A new adaptive marine policy toolbox to support ecosystem-based approach to management

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Electron flow through cytochrome P450

The cytochromes P450 (P450s) are a remarkable class of heme enzymes that catalyze the metabolism of xenobiotics and the biosynthesis of signaling molecules. Controlled electron flow into the thiolate-ligated heme active site allows P450s to activate molecular oxygen and hydroxylate aliphatic C–H bonds via the formation of high-valent metal-oxo intermediates (compounds I and II). Due to the reactive nature and short lifetimes of these intermediates, many of the fundamental steps in catalysis have not been observed directly. The Gray group and others have developed photochemical methods, known as “flash-quench,” for triggering electron transfer (ET) and generating redox intermediates in proteins in the absence of native ET partners. Photo-triggering affords a high degree of temporal precision for the gating of an ET event; the initial ET and subsequent reactions can be monitored on the nanosecond-to-second timescale using transient absorption (TA) spectroscopies. Chapter 1 catalogues critical aspects of P450 structure and mechanism, including the native pathway for formation of compound I, and outlines the development of photochemical processes that can be used to artificially trigger ET in proteins. Chapters 2 and 3 describe the development of these photochemical methods to establish electronic communication between a photosensitizer and the buried P450 heme. Chapter 2 describes the design and characterization of a Ru-P450-BM3 conjugate containing a ruthenium photosensitizer covalently tethered to the P450 surface, and nanosecond-to-second kinetics of the photo-triggered ET event are presented. By analyzing data at multiple wavelengths, we have identified the formation of multiple ET intermediates, including the catalytically relevant compound II; this intermediate is generated by oxidation of a bound water molecule in the ferric resting state enzyme. The work in Chapter 3 probes the role of a tryptophan residue situated between the photosensitizer and heme in the aforementioned Ru-P450 BM3 conjugate. Replacement of this tryptophan with histidine does not perturb the P450 structure, yet it completely eliminates the ET reactivity described in Chapter 2. The presence of an analogous tryptophan in Ru-P450 CYP119 conjugates also is necessary for observing oxidative ET, but the yield of heme oxidation is lower. Chapter 4 offers a basic description of the theoretical underpinnings required to analyze ET. Single-step ET theory is first presented, followed by extensions to multistep ET: electron “hopping.” The generation of “hopping maps” and use of a hopping map program to analyze the rate advantage of hopping over single-step ET is described, beginning with an established rhenium-tryptophan-azurin hopping system. This ET analysis is then applied to the Ru-tryptophan-P450 systems described in Chapter 2; this strongly supports the presence of hopping in Ru-P450 conjugates. Chapter 5 explores the implementation of flash-quench and other phototriggered methods to examine the native reductive ET and gas binding events that activate molecular oxygen. In particular, TA kinetics that demonstrate heme reduction on the microsecond timescale for four Ru-P450 conjugates are presented. In addition, we implement laser flash-photolysis of P450 ferrous–CO to study the rates of CO rebinding in the thermophilic P450 CYP119 at variable temperature. Chapter 6 describes the development and implementation of air-sensitive potentiometric redox titrations to determine the solution reduction potentials of a series of P450 BM3 mutants, which were designed for non-native cyclopropanation of styrene in vivo. An important conclusion from this work is that substitution of the axial cysteine for serine shifts the wild type reduction potential positive by 130 mV, facilitating reduction by biological redox cofactors in the presence of poorly-bound substrates. While this mutation abolishes oxygenation activity, these mutants are capable of catalyzing the cyclopropanation of styrene, even within the confines of an E. coli cell. Four appendices are also provided, including photochemical heme oxidation in ruthenium-modified nitric oxide synthase (Appendix A), general protocols (Appendix B), Chapter-specific notes (Appendix C) and Matlab scripts used for data analysis (Appendix D).

Transition metal clusters supported by multinucleating ligand frameworks as models of biological active sites

This dissertation describes efforts to model biological active sites with small molecule clusters. The approach used took advantage of a multinucleating ligand to control the structure and nuclearity of the product complexes, allowing the study of many different homo- and heterometallic clusters. Chapter 2 describes the synthesis of the multinucleating hexapyridyl trialkoxy ligand used throughout this thesis and the synthesis of trinuclear first row transition metal complexes supported by this framework, with an emphasis on tricopper systems as models of biological multicopper oxidases. The magnetic susceptibility of these complexes were studied, and a linear relation was found between the Cu-O(alkoxide)-Cu angles and the antiferromagnetic coupling between copper centers. The triiron(II) and trizinc(II) complexes of the ligand were also isolated and structurally characterized.

Chapter 3 describes the synthesis of a series of heterometallic tetranuclear manganese dioxido complexes with various incorporated apical redox-inactive metal cations (M = Na⁺, Ca²⁺, Sr²⁺, Zn²⁺, Y³⁺). Chapter 4 presents the synthesis of heterometallic trimanganese(IV) tetraoxido complexes structurally related to the CaMn₃ subsite of the oxygen-evolving complex (OEC) of Photosystem II. The reduction potentials of these complexes were studied, and it was found that each isostructural series displays a linear correlation between the reduction potentials and the Lewis acidities of the incorporated redox-inactive metals. The slopes of the plotted lines for both the dioxido and tetraoxido clusters are the same, suggesting a more general relationship between the electrochemical potentials of heterometallic manganese oxido clusters and their “spectator” cations. Additionally, these studies suggest that Ca²⁺ plays a role in modulating the redox potential of the OEC for water oxidation.

Chapter 5 presents studies of the effects of the redox-inactive metals on the reactivities of the heterometallic manganese complexes discussed in Chapters 3 and 4. Oxygen atom transfer from the clusters to phosphines is studied; although the reactivity is kinetically controlled in the tetraoxido clusters, the dioxido clusters with more Lewis acidic metal ions (Y³⁺ vs. Ca²⁺) appear to be more reactive. Investigations of hydrogen atom transfer and electron transfer rates are also discussed.

Appendix A describes the synthesis, and metallation reactions of a new dinucleating bis(N-heterocyclic carbene)ligand framework. Dicopper(I) and dicobalt(II) complexes of this ligand were prepared and structurally characterized. A dinickel(I) dichloride complex was synthesized, reduced, and found to activate carbon dioxide. Appendix B describes preliminary efforts to desymmetrize the manganese oxido clusters via functionalization of the basal multinucleating ligand used in the preceding sections of this dissertation. Finally, Appendix C presents some partially characterized side products and unexpected structures that were isolated throughout the course of these studies.

Optical designs for improved solar cell performance

The solar resource is the most abundant renewable resource on earth, yet it is currently exploited with relatively low efficiencies. To make solar energy more affordable, we can either reduce the cost of the cell or increase the efficiency with a similar cost cell. In this thesis, we consider several different optical approaches to achieve these goals. First, we consider a ray optical model for light trapping in silicon microwires. With this approach, much less material can be used, allowing for a cost savings. We next focus on reducing the escape of radiatively emitted and scattered light from the solar cell. With this angle restriction approach, light can only enter and escape the cell near normal incidence, allowing for thinner cells and higher efficiencies. In Auger-limited GaAs, we find that efficiencies greater than 38% may be achievable, a significant improvement over the current world record. To experimentally validate these results, we use a Bragg stack to restrict the angles of emitted light. Our measurements show an increase in voltage and a decrease in dark current, as less radiatively emitted light escapes. While the results in GaAs are interesting as a proof of concept, GaAs solar cells are not currently made on the production scale for terrestrial photovoltaic applications. We therefore explore the application of angle restriction to silicon solar cells. While our calculations show that Auger-limited cells give efficiency increases of up to 3% absolute, we also find that current amorphous silicion-crystalline silicon heterojunction with intrinsic thin layer (HIT) cells give significant efficiency gains with angle restriction of up to 1% absolute. Thus, angle restriction has the potential for unprecedented one sun efficiencies in GaAs, but also may be applicable to current silicon solar cell technology. Finally, we consider spectrum splitting, where optics direct light in different wavelength bands to solar cells with band gaps tuned to those wavelengths. This approach has the potential for very high efficiencies, and excellent annual power production. Using a light-trapping filtered concentrator approach, we design filter elements and find an optimal design. Thus, this thesis explores silicon microwires, angle restriction, and spectral splitting as different optical approaches for improving the cost and efficiency of solar cells.

Design strategies for ultra-high efficiency photovoltaics

While concentrator photovoltaic cells have shown significant improvements in efficiency in the past ten years, once these cells are integrated into concentrating optics, connected to a power conditioning system and deployed in the field, the overall module efficiency drops to only 34 to 36%. This efficiency is impressive compared to conventional flat plate modules, but it is far short of the theoretical limits for solar energy conversion. Designing a system capable of achieving ultra high efficiency of 50% or greater cannot be achieved by refinement and iteration of current design approaches.

This thesis takes a systems approach to designing a photovoltaic system capable of 50% efficient performance using conventional diode-based solar cells. The effort began with an exploration of the limiting efficiency of spectrum splitting ensembles with 2 to 20 sub cells in different electrical configurations. Incorporating realistic non-ideal performance with the computationally simple detailed balance approach resulted in practical limits that are useful to identify specific cell performance requirements. This effort quantified the relative benefit of additional cells and concentration for system efficiency, which will help in designing practical optical systems.

Efforts to improve the quality of the solar cells themselves focused on the development of tunable lattice constant epitaxial templates. Initially intended to enable lattice matched multijunction solar cells, these templates would enable increased flexibility in band gap selection for spectrum splitting ensembles and enhanced radiative quality relative to metamorphic growth. The III-V material family is commonly used for multijunction solar cells both for its high radiative quality and for the ease of integrating multiple band gaps into one monolithic growth. The band gap flexibility is limited by the lattice constant of available growth templates. The virtual substrate consists of a thin III-V film with the desired lattice constant. The film is grown strained on an available wafer substrate, but the thickness is below the dislocation nucleation threshold. By removing the film from the growth substrate, allowing the strain to relax elastically, and bonding it to a supportive handle, a template with the desired lattice constant is formed. Experimental efforts towards this structure and initial proof of concept are presented.

Cells with high radiative quality present the opportunity to recover a large amount of their radiative losses if they are incorporated in an ensemble that couples emission from one cell to another. This effect is well known, but has been explored previously in the context of sub cells that independently operate at their maximum power point. This analysis explicitly accounts for the system interaction and identifies ways to enhance overall performance by operating some cells in an ensemble at voltages that reduce the power converted in the individual cell. Series connected multijunctions, which by their nature facilitate strong optical coupling between sub-cells, are reoptimized with substantial performance benefit.

Photovoltaic efficiency is usually measured relative to a standard incident spectrum to allow comparison between systems. Deployed in the field systems may differ in energy production due to sensitivity to changes in the spectrum. The series connection constraint in particular causes system efficiency to decrease as the incident spectrum deviates from the standard spectral composition. This thesis performs a case study comparing performance of systems over a year at a particular location to identify the energy production penalty caused by series connection relative to independent electrical connection.

Marriage, transgression and death: Wuthering heights and The awakening

Esta dissertação tem como objetivo analisar a situação da vida da mulher durante o século XIX, na Inglaterra e nos Estados Unidos da América, através de duas obras do século XIX: Wuthering Heights (1847) de Emile Brontë e The Awakening (1889) de Kate Chopin. Objetivamos, na presente dissertação, apontar a crítica dos discursos patriarcal e das práticas de poder social que tornaram o contexto social das mulheres representadas nos romances citados, propício para a anulação da expressão erótica e repressão. O objeto da análise restringiu-se às duas personagens principais dos romances, Catherine Earnshaw e Edna Pontellier; personagens cujas subjetividades foram reprimidas através da imposição e desempenho de papéis sociais que não as satisfaziam como mulheres

Effects of starvation on energy density of juvenile chum salmon (Oncorhynchus keta) captured in marine waters of Southeastern Alaska

We conducted laboratory starvation experiments on juvenile chum salmon (Oncorhynchus keta) captured in the neritic marine waters of northern Southeast Alaska in June and July 2003. Temporal changes in fish energy density (whole body energy content [WBEC], cal/g dry weight), percent moisture content, wet weight (g), length (mm), and size-related condition residuals were measured in the laboratory and were then compared to long-term field data. Laboratory water temperatures and salinities averaged 9°C and 32 psu in both months. Trends in response variables were similar for both experimental groups, although sampling intervals were limited in July because fewer fish were available (n= 54) than in June (n=101). Overall, for June (45-d experimental period, 9 intervals), WBEC, wet weight, and condition residuals decreased and percent moisture content increased, whereas fork length did not change. For July (20-d experimental period, 5 intervals), WBEC and condition residuals decreased, percent moisture content and fork length increased, and wet weight did not change. WBEC, percent moisture content, and condition residuals fell outside the norm of longterm data ranges within 10–15 days of starvation, and may be more useful than fork length and wet weight for detecting fish condition responses to suboptimal environments.

Prevalence of the commensal barnacle Xenobalanus globicipitis on cetacean species in the eastern tropical Pacific Ocean, and a review of global occurrence

Distribution and prevalence of the phoretic barnacle Xenobalanus on cetacean species are reported for 22 cetaceans in the eastern tropical Pacific Ocean (21 million km2). Four cetacean species are newly reported hosts for Xenobalanus: Bryde’s whale (Balaenoptera edeni), long-beaked common dolphin (Delphinus capensis), humpback whale (Megaptera novaeangliae), and spinner dolphin (Stenella longirostris). Sightings of Xenobalanus in pelagic waters are reported for the first time, and concentrations were located within three productive zones: near the Baja California peninsula, the Costa Rica Dome and waters extending west along the 10°N Thermocline Ridge, and near Peru and the Galapagos Archipelago. Greatest prevalence was observed on blue whales (Balaenoptera musculus) indicating that slow swim speeds are not necessary for effective barnacle settlement. Overall, prevalence and prevalence per sighting were generally lower than previously reported. The number of barnacles present on an individual whale was greatest for killer whales, indicating that Xenobalanus larvae may be patchily distributed. The broad geographic distribution and large number of cetacean hosts, indicate an extremely cosmopolitan distribution. A better understanding of the biology of Xenobalanus is needed before this species can be used as a biological tag.

Biographical Sketch of Spencer Fullerton Baird

Spencer Fullerton Baird was born in Reading, Pennsylvania, February 3, 1823. In 1834 he was sent to a Quaker boarding-school kept by Dr. McGraw, at Port Deposit, Maryland, and the year following to the Reading Grammar School. In 1836 he entered Dickinson College, and was graduated at the age of seventeen. After leaving college, his time for several years was devoted to studies in general natural history, to long pedestrian excursions for the purpose of observing animals and plants and collecting specimens, and to the organization of a private cabinet of natural history, which a few years later became the nucleus of the museum of the Smithsonian Institution. During this period he published a number of original papers on natural history. He also read medicine with Dr. Middleton Goldsmith, attending a winter course of lectures at the College of Physicians and Surgeons, in New York, in 1842. His medical course was never formally completed, although in 1848 he received the degree of M. D., honoris causa, from the Philadelphia Medical College. In 1845 he was chosen professor of natural history in Dickinson College, and in 1846 his duties and emoluments were increased by election to the chair of natural history and chemistry in the same institution. In 1848 he declined a call to the professorship of natural science in the University of Vermont. In 1849 he undertook his first extensive literary work, translating and editing the text for the "Iconographic Encyclopedia," an English version of Heck's Bilder Atlas, published in connection with Brockhaus's Conversations Lexikon.

Gerenciamento de resíduos sólidos nas atividades de exploração offshore de óleo e gás.

Apesar da relevância econômica, a atividade de Exploração e Produção (E&P) é considerada potencialmente causadora de impactos ambientais, dentre estes destaca-se a geração de resíduos sólidos. Neste cenário, estão sendo criados uma série de regulamentações e acordos internacionais cada vez mais restritivos pertinentes a esta temática, dentre estes a Nota Técnica CGPEG/DILIC/IBAMA n 01/11, que estabelece a implementação do Projeto de Controle da Poluição (PCP). Além de marcos regulatórios cada vez mais rígidos, o gerenciamento de resíduos é fundamental para a minimização de impactos ambientais, pois se o mesmo não for realizado de maneira eficiente, pode gerar custos e problemas ambientais e a imagem da empresa pode ficar comprometida através de passivos ambientais. Sendo assim, o presente trabalho visa analisar o processo de Gerenciamento de Resíduos Sólidos gerados em instalações marítimas de perfuração de poços de petróleo, bem como a adequação deste processo à legislação vigente de modo a identificar os principais entraves para a minimização dos efeitos ambientais provocados pela atividade. O estabelecimento de um marco regulatório para controle da poluição dessa atividade definiu novas diretrizes, que levarão a redução dos quantitativos gerados, bem como a adoção de melhores formas para tratamento e disposição dos resíduos. Contudo, o crescimento das atividades de exploração de petróleo deverá ser acompanhado também do desenvolvimento e ampliação do mercado nacional voltado ao transporte, tratamento e disposição final de resíduos, de forma a reduzir ao máximo o impacto ambiental causado por estas atividades.

Severe droughts reduce estuarine primary productivity with cascading effects on higher trophic levels

Using a 10-yr time-series data set, we analyzed the effects of two severe droughts on water-quality and ecosystem processes in a temperate, eutrophic estuary (Neuse River Estuary, North Carolina). During the droughts, dissolved inorganic nitrogen concentrations were on average 46–68% lower than the long-term mean due to reduced riverine input. Phytoplankton productivity and biomass were slightly below average for most of the estuary during a spring–autumn drought in 2002, but were dramatically lower than average throughout the estuary during an autumn–winter drought in 2007–2008. Droughts affected upper trophic levels through alteration of both habitat condition (i.e., bottom-water dissolved oxygen levels) and food availability. Bottomwater dissolved oxygen levels were near or slightly above average during the 2002 drought and during summer 2007. Concomitant with these modest improvements in bottom-water oxygen condition, fish kills were greatly reduced relative to the long-term average. Low-oxygen bottom-water conditions were more pronounced during summer 2008 in the latter stages of the 2007–2008 drought, and mesozooplankton abundances were eight-fold lower in summer 2008 than during nondrought years. Below-average mesozooplankton abundances persisted for well over 1 yr beyond cessation of the drought. Significant fish kills were observed in summer 2008 and 2009, perhaps due to the synergistic effects of hypoxia and reduced food availability. These results indicate that droughts can exert both ephemeral and prolonged multiyear influence on estuarine ecosystem processes and provide a glimpse into the future, when many regions of the world are predicted to face increased drought frequency and severity due to climate change.

Land surface hydrology in a general circulation model: global and regional fields needed for validation

For the last two decades most general circulation models (GCMs) have included some kind of surface hydrology submodel. The content of these submodels is becoming increasingly complex and realistic. It is still easy to identify defects in present treatments. Yet, to improve our ability to model the contribution of land hydrology to climate and climate change, we must be concerned not with just the surface hydrology submodel per se, but also with how it works in the overall context of the GCM.

The stripe-backed weasel Mustela strigidorsa: taxonomy, ecology, distribution and status

1. The stripe-backed weasel Mustela strigidorsa is one of the rarest and least-known mustelids in the world. Its phylogenetic relationships with other Mustela species remain controversial, though several unique morphological features distinguish it from congeners. 2. It probably lives mainly in evergreen forests in hills and mountains, but has also been recorded from plains forest, dense scrub, secondary forest, grassland and farmland. Known sites range in altitude from 90 m to 2500 m. Data are insufficient to distinguish between habitat and altitudes which support populations, and those where only dispersing animals may occur. 3. It has been confirmed from many localities in north-east India, north and central Myanmar, south China, north Thailand, north and central Laos, and north and central Vietnam. Given the limited survey effort, the number of recent records shows that the species is not as rare as hitherto believed. Neither specific nor urgent conservation needs are apparent.