Late Transition Metals Supported by Aryl Ethers and Phenoxides Bearing Pendant Phosphines: Mechanistic Insights Relevant to Ether C-O Bond Cleavage

Terphenyl diphosphines bearing pendant ethers were prepared to provide mechanistic insight into the mechanism of activation of aryl C–O bonds with Group 9 and Group 10 transition metals. Chapters 2 and 3 of this dissertation describe the reactivity of compounds supported by the model phosphine and extension of this chemistry to heterogenous C–O bond activation.

Chapter 2 describes the synthesis and reactivity of aryl-methyl and aryl-aryl model systems. The metallation of these compounds with Ni, Pd, Pt, Co, Rh, and Ir is described. Intramolecular bond activation pathways are described. In the case of the aryl-methyl ether, aryl C–O bond activation was observed only for Ni, Rh, and Ir.

Chapter 3 outlines the reactivity of heterogenous Rh and Ir catalysts for aryl ether C–O bond cleavage. Using Rh/C and an organometallic Ir precursor, aryl ethers were treated with H2 and heat to afford products of hydrogenolysis and hydrogenation. Conditions were modified to optimize the yield of hydrogenolysis product. Hydrogenation could not be fully suppressed in these systems.

Appendix A describes initial investigations of bisphenoxyiminoquinoline dichromium compounds for selective C2H4 oligomerization to afford α-olefins. The synthesis of monometallic and bimetallic Cr complexes is described. These compounds are compared to literature examples and found to be less active and non-selective for production of α-olefins.

Appendix B describes the coordination chemistry of terphenyl diphosphines, terphenyl bisphosphinophenols, and biphenyl phosphinophenols proligands with molybdenum, cobalt, and nickel. Since their synthesis, terphenyl diphosphine molybdenum compounds have been reported to be good catalysts for the dehydrogenation of ammonia borane. Biphenyl phosphinophenols are demonstrated provide both phosphine and arene donors to transition metals while maintaining a sterically accessible coordination sphere. Such ligands may be promising in the context of the activation of other small molecules.

Appendix C contains relevant NMR spectra for the compounds presented in the preceding sections.

Efficiency, energy and stoichiometry in pelagic food webs; reciprocal roles of food quality and food quantity

In most lakes, zooplankton production is constrained by food quantity, but frequently high C:P poses an additional constraint on zooplankton production by reducing the carbon transfer efficiency from phytoplankton to zooplankton. This review addresses how the flux of matter and energy in pelagic food webs is regulated by food quantity in terms of C and its stoichiometric quality in terms of C:P. Increased levels of light, CO2 and phosphorus could each increase seston mass and, hence, food quantity for zooplankton, but while light and CO2 each cause increased C:P (i.e. reduced food quality for herbivores), increased P may increase seston mass and its stoichiometric quality by reducing C:P. Development of food quality and food quantity in response to C- or P-enrichments will differ between 'batch-type' lakes (dominated by one major, seasonal input of water and nutrients) and 'continuous-culture' types of lakes with a more steady flow-rate of water and nutrients. The reciprocal role of food quantity and stoichiometric quality will depend strongly on facilitation via grazing and recycling by the grazers, and this effect will be most important in systems with low renewal rates. At high food abundance but low quality, there will be a 'quality starvation' in zooplankton. From a management point of view, stoichiometric theory offers a general tool-kit for understanding the integrated role of C and P in food webs and how food quantity and stoichiometric quality (i.e. C:P) regulate energy flow and trophic efficiency from base to top in food webs.From a management point of view, stoichiometric theory offers a general tool-kit for understanding the integrated role of C and P in food webs and how food quantity and stoichiometric quality (i.e. C:P) regulate energy flow and trophic efficiency from base to top in food webs.

Biotic vs. Abiotic Control of Decomposition: A Comparison of the Effects of Simulated Extinctions and Changes in Temperature

The loss of species is known to have significant effects on ecosystem functioning, but only recently has it been recognized that species loss might rival the effects of other forms of environmental change on ecosystem processes. There is a need for experimental studies that explicitly manipulate species richness and environmental factors concurrently to determine their relative impacts on key ecosystem processes such as plant litter decomposition. It is crucial to understand what factors affect the rate of plant litter decomposition and the relative magnitude of such effects because the rate at which plant litter is lost and transformed to other forms of organic and inorganic carbon determines the capacity for carbon storage in ecosystems and the rate at which greenhouse gasses such as carbon dioxide are outgassed. Here we compared how an increase in water temperature of 5 degrees C and loss of detritivorous invertebrate and plant litter species affect decomposition rates in a laboratory experiment simulating stream conditions. Like some prior studies, we found that species identity, rather than species richness per se, is a key driver of decomposition, but additionally we showed that the loss of particular species can equal or exceed temperature change in its impact on decomposition. Our results indicate that the loss of particular species can be as important a driver of decomposition as substantial temperature change, but also that predicting the relative consequences of species loss and other forms of environmental change on decomposition requires knowledge of assemblages and their constituent species' ecology and ecophysiology

Growth and survival of sockeye salmon (Oncorhynchus nerka) from Karluk Lake and River, Alaska, in relation to climatic and oceanic regimes and indices, 1922–2000

We examined whether the relationship between climate and salmon production was linked through the effect of climate on the growth of sockeye salmon (Oncorhynchus nerka) at sea. Smolt length and juvenile, immature, and maturing growth rates were estimated from increments on scales of adult sockeye salmon that returned to the Karluk River and Lake system on Kodiak Island, Alaska, over 77 years, 1924–2000. Survival was higher during the warm climate regimes and lower during the cool regime. Growth was not correlated with survival, as estimated from the residuals of the Ricker stock-recruitment model. Juvenile growth was correlated with an atmospheric forcing index and immature growth was correlated with the amount of coastal precipitation, but the magnitude of winter and spring coastal downwelling in the Gulf of Alaska and the Pacific Northwest atmospheric patterns that influence the directional bifurcation of the Pacific Current were not related to the growth of Karluk sockeye salmon. However, indices of sea surface temperature, coastal precipitation, and atmospheric circulation in the eastern North Pacific were correlated with the survival of Karluk sockeye salmon. Winter and spring precipitation and atmospheric circulation are possible processes linking survival to climate variation in Karluk sockeye salmon.

Comparative study of hatching rates of African catfish (Clarias gariepinus Burchell 1822) eggs on different substrates

The hatching rates of African catfish (Clarias gariepinus) eggs on four natural substrates: the roots of Nile cabbage (Pistia stratiotes), water hyacinth (Eichhornia crassipes), pond weed (Ceratophyllum dermasum) and green grass leaves (Commelina sp.), and four artificial substrates: sisal mats, nylon mats, papyrus mats and kakaban mats, was assessed. Concrete slabs were used as control. The natural substrates performed better than the artificial ones. Pistia roots gave the best mean hatching rate of 66.2 ± 3.62%. Green grass leaves were second with a mean rate of 54.0 ± 3.46%, water hyacinth was third with 49.7 ± 3.16% and Ceratophyllum fourth with a mean of 13.0 ± 2.37%. Concrete slabs gave a mean rate of 18.6 ± 2.8%, sisal mats 18.6 ± 2.0%, papyrus 12.2 ± 1.2% and kakaban 11.8 ± 1.9%. Nylon mats were the last, with a mean rate of 4.0 ± 0.7%. The best performing natural substrates were those with the ability to float and thin fibrous roots that seemed to allow higher aeration of the eggs during incubation. The cost of using natural substrates was minimal.

Escapement of the Cape rock lobster (Jasus lalandii ) through the mesh and entrance of commercial traps

Metal-framed traps covered with polyethylene mesh used in the fishery for the South African Cape rock lobster (Jasus lalandii) incidentally capture large numbers of undersize (<75 mm CL) specimens. Air-exposure, handling, and release procedures affect captured rock lobsters and reduce the productivity of the stock, which is heavily fished. Optimally, traps should retain legalsize rock lobsters and allow sublegal animals to escape before traps are hauled. Escapement, based on lobster morphometric measurements, through meshes of 62 mm, 75 mm, and 100 mm was investigated theoretically under controlled conditions in an aquarium, and during field trials. SELECT models were used to model escapement, wherever appropriate. Size-selectivity curves based on the logistic model fitted the aquarium and field data better than asymmetrical Richards curves. The lobster length at 50% retention (L50) on the escapement curve for 100-mm mesh in the aquarium (75.5 mm CL) approximated the minimum legal size (75 mm CL); however estimates of L50 increased to 77.4 mm in field trials where trapentrances were sealed, and to 82.2 mm where trap-entrances were open. Therfore, rock lobsters that cannot escape through the mesh of sealed field traps do so through the trap entrance of open traps. By contrast, the wider selection range and lower L25 of field, compared to aquarium, trials (SR = 8.2 mm vs. 2.6 mm; L25 =73.4 mm vs. 74.1 mm), indicate that small lobsters that should be able to escape from 100-mm mesh traps do not always do so. Escapement from 62-mm mesh traps with open entrance funnels increased by 40−60% over sealed traps. The findings of this study with a known size distribution, are related to those of a recent indirect (comparative) study for the same species, and implications for trap surveys, commercial catch rates, and ghost fishing are discussed.

On the Distribution and Fishery Potential of the Japanese Red Crab Chaceon granulatus in the Palauan Archipelago, Western Caroline Islands

A deep-water trapping survey in the Palauan archipelago, Western Caroline Islands, has revealed an abundance of the Japanese red crab, Chaceon granulatus. The recorded depth range (250-900 m) is similar to that of other geryonids, but the large numbers of females caught below 700 m is atypical. Mean yields in excess of 5 kg crabs plus 1 kg shrimp, Heterocarpus laevigatus, by-catch per trap-night were attainable at optimum depths. Chaceon granulatus is apparently a very large geryonid, with maximum weights of 2.02 kg and 1.51 kg recorded for male and female specimens, respectively. A range of body colors was observed: Orange-red shades appear to dominate the deeper waters (below 500 m) while yellow-tan colors are more abundant in the upper reaches. Preliminary evidence suggests that Chaceon granulatus is highly marketable, and the infrastructure in Palau is such that crabs could either be marketed fresh locally or airfreighted to Japan as a quick-frozen product. The high post-trapping survival rates observed indicate that maintaining crabs in live-holding tanks may be a feasible option. The large catches and quality of deep-water crabs taken suggests that the Palauan population of Chaceon granulatus may be able to support a small-scale fishery. It is not yet known whether this population is unusually large or whether these findings typify the deep forereef fauna of the region.

Economic and social impacts of Integrated Aquaculture-Agriculture technologies in Bangladesh

This study estimated the adoption rate of integrated aquaculture-agriculture (IAA) technologies in Bangladesh and their impact on poverty and fish and food consumption in adopting households. We used a novel, simulation-based approach to impact assessment called Tradeoff Analysis for Multi-Dimensional Impact Assessment (TOA-MD). We used the TOA-MD model to demonstrate how it is possible to use available data to estimate adoption rates in relevant populations, and to quantify impacts on distributional outcomes such as poverty and food security, thus demonstrating ex ante the potential for further investment in technology dissemination. The analysis used baseline and end-of-project survey data from WorldFish-implemented Development of Sustainable Aquaculture Project (DSAP), promoting IAA. This dataset was used to simulate adoption and assess its impacts on poverty and food security in the target population. We found that, if adopted, IAA had a significant positive impact on reducing poverty and improving food security and income.

Ex-ante assessment of integrated aquaculture-agriculture adoption and impact in Southern Malawi

There are increasing requirements for impact assessment by development partners in order to increase the accountability and effectiveness of research and development projects. Impact assessment research has been dominated by conventional economic methods. This context challenges agricultural research organizations to develop and apply alternative impact assessment methods incorporating economic, social, and environmental impact components. In this study, we use the Tradeoff Analysis for Multi-Dimensional Impact Assessment (TOA-MD) model to evaluate the impact of integrated aquaculture-agriculture (IAA) adoption in Malawi. The study demonstrated that with a minimal data set, the TOA-MD model can be applied to predict and assess the adoption rates of new technologies and practices as well as their economic and non-economic impacts.

Earthquakes, influenza and cycles of Indian kala-azar.

It is suggested that previous data indicate 3 major epidemics of kala-azar in Assam between 1875 and 1950, with inter-epidemic periods of 30-45 and 20 years. This deviates from the popular view of regular cycles with a 10-20 year period. A deterministic mathematical model of kala-azar is used to find the simplest explanation for the timing of the 3 epidemics, paying particular attention to the role of extrinsic (drugs, natural disasters, other infectious diseases) versus intrinsic (host and vector dynamics, birth and death rates, immunity) processes in provoking the second. We conclude that, whilst widespread influenza in 1918-1919 may have magnified the second epidemic, intrinsic population processes provide the simplest explanation for its timing and synchrony throughout Assam. The model also shows that the second inter-epidemic period is expected to be shorter than the first, even in the absence of extrinsic agents, and highlights the importance of a small fraction of patients becoming chronically infectious (with post kala-azar dermal leishmaniasis) after treatment during an epidemic.

Home range and seasonal movements of Black Sea Bass (Centropristis striata) during their inshore residency at a reef in the mid-Atlantic Bight

Black Sea Bass (Centropristis striata) in the mid-Atlantic Bight undertake seasonal cross-shelf movements to occupy inshore rocky reefs and hardbottom habitats between spring and fall. Shelf-wide migrations of this stock are well documented, but movements and home ranges of fish during their inshore residency period have not been described. We tagged 122 Black Sea Bass with acoustic transmitters at a mid-Atlantic reef to estimate home-range size and factors that influence movements (>400 m) at a 46.1-km2 study site between May and November 2003. Activity of Black Sea Bass was greatest and most consistent during summer but declined rapidly in September as water temperatures at the bottom of the seafloor increased on the inner shelf. Black Sea Bass maintained relatively large home ranges that were fish-size invariant but highly variable (13.7–736.4 ha), underscoring the importance of large sample sizes in examination of population-level characteristics of mobile species with complex social interactions. On the basis of observed variations in movement patterns and the size of home ranges, we postulate the existence of groups of conspecifics that exhibit similar space-use behaviors. The group of males released earlier in the tagging period used larger home ranges than the group of males released later in our study. In addition, mean activity levels and the probability of movement among acoustic stations varied among groups of fish in a complex manner that depended on sex. These differences in movement behaviors may increase the vulnerability of male fish to passive fishing gears, further exacerbating variation in exploitation rates for this species among reefs.

Habitat availability and heterogeneity and the Indo-Pacific warm pool as predictors of marine species richness in the tropical Indo-Pacific

Range overlap patterns were observed in a dataset of 10,446 expert-derived marine species distribution maps, including 8,295 coastal fishes, 1,212 invertebrates (crustaceans and molluscs), 820 reef-building corals, 50 seagrasses and 69 mangroves. Distributions of tropical Indo-Pacific shore fishes revealed a concentration of species richness in the northern apex and central region of the Coral Triangle epicenter of marine biodiversity. This pattern was supported by distributions of invertebrates and habitat-forming primary producers. Habitat availability, heterogeneity and sea surface temperatures were highly correlated with species richness across spatial grains ranging from 23,000 to 5,100,000 km2 with and without correction for autocorrelation. The consistent retention of habitat variables in our predictive models supports the area of refuge hypothesis which posits reduced extinction rates in the Coral Triangle. This does not preclude support for a center of origin hypothesis that suggests increased speciation in the region may contribute to species richness. In addition, consistent retention of sea surface temperatures in models suggests that available kinetic energy may also be an important factor in shaping patterns of marine species richness. Kinetic energy may hasten rates of both extinction and speciation. The position of the Indo-Pacific Warm Pool to the east of the Coral Triangle in central Oceania and a pattern of increasing species richness from this region into the central and northern parts of the Coral Triangle suggests peripheral speciation with enhanced survival in the cooler parts of the Coral Triangle that also have highly concentrated available habitat. These results indicate that conservation of habitat availability and heterogeneity is important to reduce extinction and that changes in sea surface temperatures may influence the evolutionary potential of the region.

Age, growth and mortality of the toadfish, Halobatrachus didactylus (Schneider, 1801) (Pisces: Batrachoididae), in the Bay of Cádiz (southwestern Spain)

Age, growth and mortality of the toadfish, Halobatrachus didactylus, were determined by examination of the whole sagittal otoliths of fish sampled in the Bay of Cádiz (southwestern Spain) from March 1999 to March 2000. A total of 844 specimens (425 males, 416 females, and 3 of indeterminate sex), ranging from 95 to 470 mm in total length were examined. Eighty-nine percent of the otoliths could be read allowing an age estimation. The opaque zone was formed between April and May coincident with the maximum reproductive peak, while the translucent zone formed mainly in summer-fall (June to December). Maximum ages for males and females were 12 and 10 years, respectively. The samples were dominated by 2- to 6-year-old specimens. Males matured at an age of approximately 2 years and females at 3 years. Fish total length and otolith radius were closely related. The von Bertalanffy growth curve was used to describe growth. The parameters were derived from back-calculated length-at-age. Significant differences in the growth parameters were found between sexes. Although the growth analysis revealed that this species is slow-growing, males reached larger sizes than females. Females appeared to experience higher natural mortality rates than males.