Rapid recreation assessment: a tool to assess visitor use and associated impacts at coastal and marine protected areas

As more people discover coastal and marine protected areas as destinations for leisure-time pursuits, the task of managing coastal resources while providing opportunities for high quality visitor experiences becomes more challenging. Many human impacts occur at these sites; some are caused by recreation and leisure activities on-site, and others by activities such as agriculture, aquaculture, or residential and economic development in surrounding areas. Coastal management professionals are continually looking for effective ways to prevent or mitigate negative impacts of visitor use. (PDF contains 8 pages) Most coastal and marine protected area managers are challenged with balancing two competing goals—protection of natural and cultural resources and provision of opportunities for public use. In most cases, some level of compromise between the goals is necessary, where one goal constrains or “outweighs” the other. Often there is a lack of clear agreement about the priority of these competing goals. Consequently, while natural resource decisions should ultimately be science-based and objective, such decisions are frequently made under uncertainty, relying heavily upon professional judgment. These decisions are subject to a complex array of formal and informal drivers and constraints—data availability, timing, legal mandate, political will, diverse public opinion, and physical, human, and social capital. This paper highlights assessment, monitoring, and planning approaches useful to gauge existing resource and social conditions, determine feasibility of management actions, and record decision process steps to enhance defensibility. Examples are presented from pilot efforts conducted at the Rookery Bay National Estuarine Research Reserve (NERR) and Ten Thousand Islands National Wildlife Refuge (NWR) in South Florida.

Genetic and morphological identification of pelagic juvenile rockfish collected from the Gulf of Alaska

Pelagic juvenile rockfish (Sebastes spp.) collected in surveys designed to assess juvenile salmonids and other species in the Gulf of Alaska in 1998 and 2000–2003 provide an opportunity to document the occurrence of the pelagic juveniles of several species of rockfish. Often, species identification of rockfish is difficult or impossible at this stage of development (~20 to 60 mm), and few species indigenous to Alaska waters have been described. Use of mitochondrial DNA markers for rockfish species allowed unequivocal identification of ten species (S. aleutianus, S. alutus, S. borealis, S. entomelas, S. flavidus, S. melanops, S. pinniger, S. proriger, S. reedi, and S. ruberrimus) in subsamples from the collections. Other specimens were genetically assignable to groups of two or three species. Sebastes borealis, S. crameri, and S. reedi were identified using morphological data. Combining genetic and morphological data allowed successful resolution of the other species as S. emphaeus, probably S. ciliatus (although S. polyspinis cannot be totally ruled out), and S. polyspinis. Many specimens were initially morphologically indistinguishable from S. alutus, and several morphological groups included fish genetically identified as S. alutus. This paper details the characteristics of these pelagic juveniles to facilitate morphological identification of these species in future collections. (PDF file contains 32 pages.)

Seasonal, horizontal, and vertical distribution of phytoplankton chlorophyll a in the Northeast U.S. Continental Shelf Ecosystem

The broad scale features in the horizontal, vertical, and seasonal distribution of phytoplankton chlorophyll a on the northeast U.S. continental shelf are described based on 57,088 measurements made during 78 oceanographic surveys from 1977 through 1988. Highest mean water column chlorophyll concentration (Chlw,) is usually observed in nearshore areas adjacent to the mouths of the estuaries in the Middle Atlantic Bight (MAB), over the shallow water on Georges Bank, and a small area sampled along the southeast edge of Nantucket Shoals. Lowest Chlw «0.125 ug l-1) is usually restricted to the most seaward stations sampled along the shelf-break and the central deep waters in the Gulf of Maine. There is at least a twofold seasonal variation in phytoplankton biomass in all areas, with highest phytoplankton concentrations (m3) and highest integrated standing stocks (m2) occurring during the winter-spring (WS) bloom, and the lowest during summer, when vertical density stratification is maximal. In most regions, a secondary phytoplankton biomass pulse is evident during convective destratification in fall, usually in October. Fall bloom in some areas of Georges Bank approaches the magnitude of the WS-bloom, but Georges Bank and Middle Atlantic Bight fall blooms are clearly subordinate to WS-blooms. Measurements of chlorophyll in two size-fractions of the phytoplankton, netplankton (>20 um) and nanoplankton «20 um), revealed that the smaller nanoplankton are responsible for most of the phytoplankton biomass on the northeast U.S. shelf. Netplankton tend to be more abundant in nearshore areas of the MAB and shallow water on Georges Bank, where chlorophyll a is usually high; nanoplankton dominate deeper water at the shelf-break and deep water in the Gulf of Maine, where Chlw is usually low. As a general rule, the percent of phytoplankton in the netplankton size-fraction increases with increasing depth below surface and decreases proceeding offshore. There are distinct seasonal and regional patterns in the vertical distribution of chlorophyll a and percent netplankton, as revealed in composite vertical profiles of chlorophyll a constructed for 11 layers of the water column. Subsurface chlorophyll a maxima are ubiquitous during summer in stratified water. Chlorophyll a in the subsurface maximum layer is generally 2-8 times the concentration in the overlying and underlying water and approaches 50 to 75% of the levels observed in surface water during WS-bloom. The distribution of the ratio of the subsurface maximum chlorophyll a to surface chlorophyll a (SSR) during summer parallels the shelfwide pattern for stability, indexed as the difference in density (sigma-t) between 40 m and surface (stability 40. The weakest stability and lowest SSR's are found in shallow tidally-mixed water on Georges Bank; the greatest stability and highest SSR's (8-12:1) are along the mid and outer MAB shelf, over the winter residual water known as the "cold band." On Georges Bank, the distribution of SSR and the stability40 are roughly congruent with the pattern for maximum surface tidal current velocity, with values above 50 cms-1 defining SSR's less than 2:1 and the well-mixed area. Physical factors (bathymetry, vertical mixing by strong tidal currents, and seasonal and regional differences in the intensity and duration of vertical stratification) appear to explain much of the variability in phytoplankton chlorophyll a throughout this ecosystem. (PDF file contains 126 pages.)

Stock Composition of Some Sockeye Salmon, Oncorhynchus nerka, Catches in Southeast Alaska, Based on Incidence of Allozyme Variants, Freshwater Ages, and a Brain-Tissue Parasite

The incidence of four discrete characters of individual sockeye salmon -two genetically inherited proteins (PGM-1*and PGM-2*), freshwater age at migration, and the presence of the brain-tissue parasite Myxobolus arcticus-in weekly samples from two Alaskan fisheries (Noyes Island in 1986 and Sumner Strait in 1987) were used to infer stock composition of the catches based on corresponding character samples from 73 Alaskan and Canadian stocks. Estimated contributions of 13 stock groups, formed on the basis of character similarity of their members, were roughly consistent with expectations from tagging experiments, knowledge of stock magnitudes, and similar assessments from scales. Imprecision of the estimated contributions by the 13 stock groups limited their practical value; but variability was much reduced for combined estimated contributions by two inclusive categories, namely stock groups whose members had either high or low brainparasite prevalence. Noyes Island catches consisted predominantly of unparasitized fish, most of which were probably of Canadian origin. The majority of Sumner Strait catches consisted of parasitized fish, whose freshwater origins may have been in Alaska or Canada. (PDF file contains 27 pages.)

Marine Debris Survey Manual

Over the last several years, concern has increased about the amount of man-made materials lost or discarded at sea and the potential impacts to the environment. The scope of the problem depends on the amounts and types of debris. One problem in making a regional comparison of debris is the lack of a standard methodology. The objective of this manual is to discuss designs and methodologies for assessment studies of marine debris. This manual has been written for managers, researchers, and others who are just entering this area of study and who seek guidance in designing marine debris surveys. Active researchers will be able to use this manual along with applicable references herein as a source for design improvement. To this end, the authors have synthesized their work and reviewed survey techniques that have been used in the past for assessing marine debris, such as sighting surveys, beach surveys, and trawl surveys, and have considered new methods (e.g., aerial photography). All techniques have been put into a general survey planning framework to assist in developing different marine debris surveys. (PDF file contains 100 pages.)

Proceedings of the International Workshop on age determination of oceanic pelagic fishes: Tunas, billfishes, and sharks, Miami, Florida, February 15-18,1982

Accurate and precise estimates of age and growth rates are essential parameters in understanding the population dynamics of fishes. Some of the more sophisticated stock assessment models, such as virtual population analysis, require age and growth information to partition catch data by age. Stock assessment efforts by regulatory agencies are usually directed at specific fisheries which are being heavily exploited and are suspected of being overfished. Interest in stock assessment of some of the oceanic pelagic fishes (tunas, billfishes, and sharks) has developed only over the last decade, during which exploitation has increased steadily in response to increases in worldwide demand for these resources. Traditionally, estimating the age of fishes has been done by enumerating growth bands on skeletal hardparts, through length frequency analysis, tag and recapture studies, and raising fish in enclosures. However, problems related to determining the age of some of the oceanic pelagic fishes are unique compared with other species. For example, sampling is difficult for these large, highly mobile fishes because of their size, extensive distributions throughout the world's oceans, and for some, such as the marlins, infrequent catches. In addition, movements of oceanic pelagic fishes often transect temperate as well as tropical oceans, making interpretation of growth bands on skeletal hardparts more difficult than with more sedentary temperate species. Many oceanic pelagics are also long-lived, attaining ages in excess of 30 yr, and more often than not, their life cycles do not lend themselves easily to artificial propagation and culture. These factors contribute to the difficulty of determining ages and are generally characteristic of this group-the tunas, billfishes, and sharks. Accordingly, the rapidly growing international concern in managing oceanic pelagic fishes, as well as unique difficulties in ageing these species, prompted us to hold this workshop. Our two major objectives for this workshop are to: I) Encourage the interchange of ideas on this subject, and 2) establish the "state of the art." A total of 65 scientists from 10 states in the continental United States and Hawaii, three provinces in Canada, France, Republic of Senegal, Spain, Mexico, Ivory Coast, and New South Wales (Australia) attended the workshop held at the Southeast Fisheries Center, Miami, Fla., 15-18 February 1982. Our first objective, encouraging the interchange of ideas, is well illustrated in the summaries of the Round Table Discussions and in the Glossary, which defines terms used in this volume. The majority of the workshop participants agreed that the lack of validation of age estimates and the means to accomplish the same are serious problems preventing advancements in assessing the age and growth of fishes, particularly oceanic pelagics. The alternatives relating to the validation problem were exhaustively reviewed during the Round Table Discussions and are a major highlight of this workshop. How well we accomplished our second objective, to establish the "state of the art" on age determination of oceanic pelagic fishes, will probably best be judged on the basis of these proceedings and whether future research efforts are directed at the problem areas we have identified. In order to produce high-quality papers, workshop participants served as referees for the manuscripts published in this volume. Several papers given orally at the workshop, and included in these proceedings, were summarized from full-length manuscripts, which have been submitted to or published in other scientific outlets-these papers are designated as SUMMARY PAPERS. In addition, the SUMMARY PAPER designation was also assigned to workshop papers that represented very preliminary or initial stages of research, cursory progress reports, papers that were data shy, or provide only brief reviews on general topics. Bilingual abstracts were included for all papers that required translation. We gratefully acknowledge the support of everyone involved in this workshop. Funding was provided by the Southeast Fisheries Center, and Jack C. Javech did the scientific illustrations appearing on the cover, between major sections, and in the Glossary. (PDF file contains 228 pages.)

Water in silicate glasses

The speciation of water in a variety of hydrous silicate glasses, including simple and rhyolitic compositions, synthesized over a range of experimental conditions with up to 11 weight percent water has been determined using infrared spectroscopy. This technique has been calibrated with a series of standard glasses and provides a precise and accurate method for determining the concentrations of molecular water and hydroxyl groups in these glasses.

For all the compositions studied, most of the water is dissolved as hydroxyl groups at total water contents less than 3-4 weight percent; at higher total water contents, molecular water becomes the dominant species. For total water contents above 3-4 weight percent, the amount of water dissolved as hydroxyl groups is approximately constant at about 2 weight percent and additional water is incorporated as molecular water. Although there are small but measurable differences in the ratio of molecular water to hydroxyl groups at a given total water content among these silicate glasses, the speciation of water is similar over this range of composition. The trends in the concentrations of the H-bearing species in the hydrous glasses included in this study are similar to those observed in other silicate glasses using either infrared or NMR spectroscopy.

The effects of pressure and temperature on the speciation of water in albitic glasses have been investigated. The ratio of molecular water to hydroxyl groups at a given total water content is independent of the pressure and temperature of equilibration for albitic glasses synthesized in rapidly quenching piston cylinder apparatus at temperatures greater than 1000°C and pressures greater than 8 kbar. For hydrous glasses quenched from melts cooled at slower rates (i.e., in internally heated or in air-quench cold seal pressure vessels), there is an increase in the ratio of molecular water to hydroxyl group content that probably reflects reequilibration of the melt to lower temperatures during slow cooling.

Molecular water and hydroxyl group concentrations in glasses provide information on the dissolution mechanisms of water in silicate liquids. Several mixing models involving homogeneous equilibria of the form H_2O + O = 20H among melt species have been explored for albitic melts. These models can account for the measured species concentrations if the effects of non-ideal behavior or mixing of polymerized units are included, or by allowing for the presence of several different types of anhydrous species.

A thermodynamic model for hydrous albitic melts has been developed based on the assumption that the activity of water in the melt is equal to the mole fraction of molecular water determined by infrared spectroscopy. This model can account for the position of the watersaturated solidus of crystalline albite, the pressure and temperature dependence of the solubility of water in albitic melt, and the volumes of hydrous albitic melts. To the extent that it is successful, this approach provides a direct link between measured species concentrations in hydrous albitic glasses and the macroscopic thermodynamic properties of the albite-water system.

The approach taken in modelling the thermodynamics of hydrous albitic melts has been generalized to other silicate compositions. Spectroscopic measurements of species concentrations in rhyolitic and simple silicate glasses quenched from melts equilibrated with water vapor provide important constraints on the thermodynamic properties of these melt-water systems. In particular, the assumption that the activity of water is equal to the mole fraction of molecular water has been tested in detail and shown to be a valid approximation for a range of hydrous silicate melts and the partial molar volume of water in these systems has been constrained. Thus, the results of this study provide a useful thermodynamic description of hydrous melts that can be readily applied to other melt-water systems for which spectroscopic measurements of the H-bearing species are available.

The biological sense of smell: olfactory search behavior and a metabolic view for olfactory perception

Part I of the thesis describes the olfactory searching and scanning behaviors of rats in a wind tunnel, and a detailed movement analysis of terrestrial arthropod olfactory scanning behavior. Olfactory scanning behaviors in rats may be a behavioral correlate to hippocampal place cell activity.

Part II focuses on the organization of olfactory perception, what it suggests about a natural order for chemicals in the environment, and what this in tum suggests about the organization of the olfactory system. A model of odor quality space (analogous to the "color wheel") is presented. This model defines relationships between odor qualities perceived by human subjects based on a quantitative similarity measure. Compounds containing Carbon, Nitrogen, or Sulfur elicit odors that are contiguous in this odor representation, which thus allows one to predict the broad class of odor qualities a compound is likely to elicit. Based on these findings, a natural organization for olfactory stimuli is hypothesized: the order provided by the metabolic process. This hypothesis is tested by comparing compounds that are structurally similar, perceptually similar, and metabolically similar in a psychophysical cross-adaptation paradigm. Metabolically similar compounds consistently evoked shifts in odor quality and intensity under cross-adaptation, while compounds that were structurally similar or perceptually similar did not. This suggests that the olfactory system may process metabolically similar compounds using the same neural pathways, and that metabolic similarity may be the fundamental metric about which olfactory processing is organized. In other words, the olfactory system may be organized around a biological basis.

The idea of a biological basis for olfactory perception represents a shift in how olfaction is understood. The biological view has predictive power while the current chemical view does not, and the biological view provides explanations for some of the most basic questions in olfaction, that are unanswered in the chemical view. Existing data do not disprove a biological view, and are consistent with basic hypotheses that arise from this viewpoint.

Photodissociation and reaction dynamics of chlorine-containing species important in stratospheric ozone chemistry

Chlorine oxide species have received considerable attention in recent years due to their central role in the balance of stratospheric ozone. Many questions pertaining to the behavior of such species still remain unanswered and plague the ability of researchers to develop accurate chemical models of the stratosphere. Presented in this thesis are three experiments that study various properties of some specific chlorine oxide species.

In the first chapter, the reaction between ClONO_2 and protonated water clusters is investigated to elucidate a possible reaction mechanism for the heterogeneous reaction of chlorine nitrate on ice. The ionic products were various forms of protonated nitric acid, NO_2 +(H_20)_m, m = 0, 1, 2. These products are analogous to products previously reported in the literature for the neutral reaction occurring on ice surfaces. Our results support the hypothesis that the heterogeneous reaction is acid-catalyzed.

In the second chapter, the photochemistry of ClONO_2 was investigated at two wavelengths, 193 and 248 nm, using the technique of photofragmentation translational spectroscopy. At both wavelengths, the predominant dissociation pathways were Cl + NO_3 and ClO + NO_2. Channel assignments were confirmed by momentum matching the counterfragments from each channel. A one-dimensional stratospheric model using the new 248 nm branching ratio determined how our results would affect the predicted Cl_x and NO_x partitioning in the stratosphere.

Chapter three explores the photodissociation dynamics of Cl_2O at 193, 248 and 308 nm. At 193 nm, we found evidence for the concerted reaction channel, Cl_2 + O. The ClO + Cl channel was also accessed, however, the majority of the ClO fragments were formed with sufficient internal energies for spontaneous secondary dissociation to occur. At 248 and 308 nm, we only observed only the ClO + Cl channel. . Some of the ClO formed at 248 nm was formed internally hot and spontaneously dissociated. Bimodal translational energy distributions of the ClO and Cl products indicate two pathways leading to the same product exist.

Appendix A, B and C discuss the details of data analysis techniques used in Chapters 1 and 2. The development of a molecular beam source of ClO dimer is presented in Appendix D.

Investigations of secondary organic aerosol formation in laboratory chambers

Secondary organic aerosol (SOA) is produced in the atmosphere by oxidation of volatile organic compounds. Laboratory chambers are used understand the formation mechanisms and evolution of SOA formed under controlled conditions. This thesis presents studies of SOA formed from anthropogenic and biogenic precursors and discusses the effects of chamber walls on suspended vapors and particles.

During a chamber experiment, suspended vapors and particles can interact with the chamber walls. Particle wall loss is relatively well-understood, but vapor wall losses have received little study. Vapor wall loss of 2,3-epoxy-1,4-butanediol (BEPOX) and glyoxal was identified, quantified, and found to depend on chamber age and relative humidity.

Particles reside in the atmosphere for a week or more and can evolve chemically during that time period, a process termed aging. Simulating aging in laboratory chambers has proven to be challenging. A protocol was developed to extend the duration of a chamber experiment to 36 h of oxidation and was used to evaluate aging of SOA produced from m-xylene. Total SOA mass concentration increased and then decreased with increasing photooxidation suggesting a transition from functionalization to fragmentation chemistry driven by photochemical processes. SOA oxidation, measured as the bulk particle elemental oxygen-to-carbon ratio and fraction of organic mass at m/z 44, increased continuously starting after 5 h of photooxidation.

The physical state and chemical composition of an organic aerosol affect the mixing of aerosol components and its interactions with condensing species. A laboratory chamber protocol was developed to evaluate the mixing of SOA produced sequentially from two different sources by heating the chamber to induce particle evaporation. Using this protocol, SOA produced from toluene was found to be less volatile than that produced from a-pinene. When the two types of SOA were formed sequentially, the evaporation behavior most closely represented that of SOA from the second parent hydrocarbon, suggesting that the structure of the mixed SOA particles resembles a core of SOA from the first precursor coated by a layer of SOA from the second precursor, indicative of limiting mixing.

Identification of thermally-tagged coherent structures in the zero pressure gradient turbulent boundary layer

A zero pressure gradient boundary layer over a flat plate is subjected to step changes in thermal condition at the wall, causing the formation of internal, heated layers. The resulting temperature fluctuations and their corresponding density variations are associated with turbulent coherent structures. Aero-optical distortion occurs when light passes through the boundary layer, encountering the changing index of refraction resulting from the density variations. Instantaneous measurements of streamwise velocity, temperature and the optical deflection angle experienced by a laser traversing the boundary layer are made using hot and cold wires and a Malley probe, respectively. Correlations of the deflection angle with the temperature and velocity records suggest that the dominant contribution to the deflection angle comes from thermally-tagged structures in the outer boundary layer with a convective velocity of approximately 0.8U∞. An examination of instantaneous temperature and velocity and their temporal gradients conditionally averaged around significant optical deflections shows behavior consistent with the passage of a heated vortex. Strong deflections are associated with strong negative temperature gradients, and strong positive velocity gradients where the sign of the streamwise velocity fluctuation changes. The power density spectrum of the optical deflections reveals associated structure size to be on the order of the boundary layer thickness. A comparison to the temperature and velocity spectra suggests that the responsible structures are smaller vortices in the outer boundary layer as opposed to larger scale motions. Notable differences between the power density spectra of the optical deflections and the temperature remain unresolved due to the low frequency response of the cold wire.

Carbon-carbon bond forming reactions from bis(carbene)-platinum(II) complexes and olefin polymerization and oligomerization using group 4 post-metallocene complexes

A long-standing challenge in transition metal catalysis is selective C–C bond coupling of simple feedstocks, such as carbon monoxide, ethylene or propylene, to yield value-added products. This work describes efforts toward selective C–C bond formation using early- and late-transition metals, which may have important implications for the production of fuels and plastics, as well as many other commodity chemicals.

The industrial Fischer-Tropsch (F-T) process converts synthesis gas (syngas, a mixture of CO + H₂) into a complex mixture of hydrocarbons and oxygenates. Well-defined homogeneous catalysts for F-T may provide greater product selectivity for fuel-range liquid hydrocarbons compared to traditional heterogeneous catalysts. The first part of this work involved the preparation of late-transition metal complexes for use in syngas conversion. We investigated C–C bond forming reactions via carbene coupling using bis(carbene)platinum(II) compounds, which are models for putative metal–carbene intermediates in F-T chemistry. It was found that C–C bond formation could be induced by either (1) chemical reduction of or (2) exogenous phosphine coordination to the platinum(II) starting complexes. These two mild methods afforded different products, constitutional isomers, suggesting that at least two different mechanisms are possible for C–C bond formation from carbene intermediates. These results are encouraging for the development of a multicomponent homogeneous catalysis system for the generation of higher hydrocarbons.

A second avenue of research focused on the design and synthesis of post-metallocene catalysts for olefin polymerization. The polymerization chemistry of a new class of group 4 complexes supported by asymmetric anilide(pyridine)phenolate (NNO) pincer ligands was explored. Unlike typical early transition metal polymerization catalysts, NNO-ligated catalysts produce nearly regiorandom polypropylene, with as many as 30-40 mol % of insertions being 2,1-inserted (versus 1,2-inserted), compared to <1 mol % in most metallocene systems. A survey of model Ti polymerization catalysts suggests that catalyst modification pathways that could affect regioselectivity, such as C–H activation of the anilide ring, cleavage of the amine R-group, or monomer insertion into metal–ligand bonds are unlikely. A parallel investigation of a Ti–amido(pyridine)phenolate polymerization catalyst, which features a five- rather than a six-membered Ti–N chelate ring, but maintained a dianionic NNO motif, revealed that simply maintaining this motif was not enough to produce regioirregular polypropylene; in fact, these experiments seem to indicate that only an intact anilide(pyridine)phenolate ligated-complex will lead to regioirregular polypropylene. As yet, the underlying causes for the unique regioselectivity of anilide(pyridine)phenolate polymerization catalysts remains unknown. Further exploration of NNO-ligated polymerization catalysts could lead to the controlled synthesis of new types of polymer architectures.

Finally, we investigated the reactivity of a known Ti–phenoxy(imine) (Ti-FI) catalyst that has been shown to be very active for ethylene homotrimerization in an effort to upgrade simple feedstocks to liquid hydrocarbon fuels through co-oligomerization of heavy and light olefins. We demonstrated that the Ti-FI catalyst can homo-oligomerize 1-hexene to C₁₂ and C₁₈ alkenes through olefin dimerization and trimerization, respectively. Future work will include kinetic studies to determine monomer selectivity by investigating the relative rates of insertion of light olefins (e.g., ethylene) vs. higher α-olefins, as well as a more detailed mechanistic study of olefin trimerization. Our ultimate goal is to exploit this catalyst in a multi-catalyst system for conversion of simple alkenes into hydrocarbon fuels.

Synthetic, kinetic and mechanistic studies in early transition metal systems. I. α- and β-hydrogen elimination reactions in derivatives of permethyltitanocene, -zirconocene, and -hafnocene. II. The reactions of aluminum alkyls with derivatives of permethylniobocene

The thermal decomposition of Cp*Ti(CH_3)_2 (Cp*≡ ƞ^5-C_5Me_5) toluene solution follows cleanly first-order kinetics and produces a single titanium product Cp*(C_5Me_4CH_2)Ti(CH_3) concurrent with the evolution of one equivalent of methane. Labeling studies using Cp*_2Ti- (CD_3)_2 and (Cp*-d_(15))_2Ti(CH_3)_2 show the decomposition to be intramolecular and the methane to be produced by the coupling of a methyl group with a hydrogen from the other TiCH_3 group. Activation parameters, ΔH^‡ and ΔS^‡, and kinetic deuterium isotope effects have been measured. The alternative decomposition pathways of α-hydrogen abstraction and a-hydrogen elimination, both leading to a titanium-methylidene intermediate, are discussed.

The insertion of unactivated acetylenes into the metal-hydride bonds of Cp*_2MH_2 (M = Zr, Hf) proceeds rapidly at low temperature to form monoand/ or bisinsertion products, dependent upon the steric bulk of the acetylene substituents. Cp*_2M(H)(C(Me)=CHMe), Cp*_2M(H)(CH=CHCMe_3), Cp*_2M(H)-(CH=CHPh), Cp*_2M(CH=CHPh)_2, Cp*_2M(CH=CHCH_3)_2 and Cp*_2Zr- (CH=CHCH_2CH_3)_2 have been isolated and characterized. To extend the study of unsaturated-carbon ligands, Cp*_2M(C≡CCH_3)_2 have been prepared by treating Cp*_2MCl_2 with LiC≡CCH_3. The reactivity of many of these complexes with carbon monoxide and dihydrogen is surveyed. The mono(2- butenyl) complexes Cp*_2M(H)(C(Me)=CHMe) rearrange at room temperature, forming the crotyl-hydride species Cp*_2M(H)(ƞ^3-C_4H_7). The bis(propenyl) and bis(l-butenyl) zirconium complexes Cp*_2Zr(CH=CHR)_2 (R = CH_3, CH_2CH_3) also rearrange, forming zirconacyclopentenes. Labeling studies, reaction chemistry, and kinetic measurements, including deuterium isotope effects, demonstrate that the unusual 6-hydrogen elimination from an sp^2-hybridized carbon is the first step in these latter rearrangements but is not observed in the former. Details of these mechanisms and the differences in reactivity of the zirconium and hafnium complexes are discussed.

The reactions of hydride- and alkyl-carbonyl derivatives of permethylniobocene with equimolar amounts of trialkylaluminum reagents occur rapidly producing the carbonyl adducts Cp*_2Nb(R)(COAlR'_3) (R = H, CH_3, CH_2CH_3, CH_2CH_2Ph, C(Me)=CHMe; R' = Me, Et). The hydride adduct Cp*_2NbH_3•AlEt_3 has also been formed. In solution, each of these compounds exists in equilibrium with the uncomplexed species. The formation constants for Cp*_2Nb(H)(COA1R'_R) have been measured. They indicate the steric bulk of the Cp* ligands plays a deciding factor in the isolation of the first example of an aluminum Lewis acid bound to a carbonyl-oxygen in preference to a metalhydride. Reactions of Cp*_2Nb(H)CO with other Lewis acids and of the one:one adducts with H_2, CO and C_2H_4 are also discussed.

Cp*_2Nb(H)(C_2H_4) also reacts with equimolar amounts of trialkylaluminum reagents, forming a one:one complex that ^1H NMR spectroscopy indicates contains a Nb-CH_2CH_2-Al bridge. This adduct also exists in equilibrium with the uncomplexed species in solution. The formation constant for Cp*_2N+/b(H)(CH_2CH_2ĀlEt_3) has been measured. Reactions of Cp*_2Nb(H)(C_2H_4) with other Lewis acids and the reactions of Cp*_2N+b(H)- (CH_2CH_2ĀlEt_3) with CO and C_2H_4 are described, as are the reactions of Cp_*2Nb(H)(CH_2=CHR) (R = Me, Ph), Cp*_2Nb(H)(CH_3C≡CCH_3) and Cp*_2Ti-(C_2H_4) with AlEt_3.

Investigations of the origin of stereocontrol in syndiospecific Ziegler-Natta polymerizations

In order to expand our understanding of the mechanism of stereocontrol in syndiospecific α-olefin polymerization, a family of Cs-symmetric, ansa-group 3 metallocenes was targeted as polymerization catalysts. The syntheses of new ansa-yttrocene and scandocene derivatives that employ the doubly [SiMe₂]- bridged ligand array (1,2-SiMe₂)₂{C₅H-3,5-(CHMe₂)₂} (where R = t- butyl, tBuThp; where R = i-propyl, iPrThp) are described. The structures of tBuThpY(µ-Cl)₂K(THF)₂, tBuThpSc(µ-Cl)₂K(Et₂O)₂, tBuThpYCH(SiMe₃)₂, Y₂{µ₂-(tBuThp)₂}(µ₂-H)₂, and tBuThpSc(µ-CH₃)₂ have been examined by single crystal X-ray diffraction methods. Ansa-yttrocenes and scandocenes that incorporate the singly [CPh₂]-bridged ligand array (CPh₂)(C₅H₄)(C₁₃H₈)(where C₅H₄ = Cp, cyclopentadienyl; where C₁₃H₈ = Flu, fluourenyl) have also been prepared. Select meallocene alkyl complexes are active single component catalysts for homopolymerization of propylene and 1-pentene. The scandocene tetramethylaluminate complexes generate polymers with the highes molecular weights of the series. Under all conditions examined atactic polymer microstructures are observed, suggesting a chain-end mechanism for stereocontrol.

A series of ansa-tantalocenes have been prepared as models for Ziegler-Natta polymerization catalysts. A singly bridged ansa-tantalocene trimethyl complex, Me₂Si(η⁵-C₅H₄)₂TaMe₃, has been prepared and used for the synthesis of a tantalocene ethylene-methyl complex. Addition of propylene to this ethylene-methyl adduct results in olefin exchange to give a mixture of endo and exo propylene isomers. Doubly-silylene bridged ansa-tantalocene complexes have been prepared with the tBuThp ligand; a tantalocene trimethyl complex and a tantalocene methylidene-methyl complex have been synthesized and characterized by X-ray diffraction. Thermolysis of the methylidene-methyl complex affords the corresponding ethylene-hydride complex. Addition of either propylene or styrene to this ethylene-hydride compound results in olefin exchange. In both cases, only one product isomer is observed. Studies of olefin exchange with ansa-tantalocene olefin-hydride and olefin-methyl complexes have provided information about the important steric influences for olefin coordination in Ziegler-Natta polymerization.

Towards understanding the mixing characteristics of turbulent buoyant flows

This work proposes a new simulation methodology in which variable density turbulent flows can be studied in the context of a mixing layer with or without the presence of gravity. Specifically, this methodology is developed to probe the nature of non-buoyantly-driven (i.e. isotropically-driven) or buoyantly-driven mixing deep inside a mixing layer. Numerical forcing methods are incorporated into both the velocity and scalar fields, which extends the length of time over which mixing physics can be studied. The simulation framework is designed to allow for independent variation of four non-dimensional parameters, including the Reynolds, Richardson, Atwood, and Schmidt numbers. Additionally, the governing equations are integrated in such a way to allow for the relative magnitude of buoyant energy production and non-buoyant energy production to be varied.

The computational requirements needed to implement the proposed configuration are presented. They are justified in terms of grid resolution, order of accuracy, and transport scheme. Canonical features of turbulent buoyant flows are reproduced as validation of the proposed methodology. These features include the recovery of isotropic Kolmogorov scales under buoyant and non-buoyant conditions, the recovery of anisotropic one-dimensional energy spectra under buoyant conditions, and the preservation of known statistical distributions in the scalar field, as found in other DNS studies.

This simulation methodology is used to perform a parametric study of turbulent buoyant flows to discern the effects of varying the Reynolds, Richardson, and Atwood numbers on the resulting state of mixing. The effects of the Reynolds and Atwood numbers are isolated by looking at two energy dissipation rate conditions under non-buoyant (variable density) and constant density conditions. The effects of Richardson number are isolated by varying the ratio of buoyant energy production to total energy production from zero (non-buoyant) to one (entirely buoyant) under constant Atwood number, Schmidt number, and energy dissipation rate conditions. It is found that the major differences between non-buoyant and buoyant turbulent flows are contained in the transfer spectrum and longitudinal structure functions, while all other metrics are largely similar (e.g. energy spectra, alignment characteristics of the strain-rate tensor). Also, despite the differences noted between fully buoyant and non-buoyant turbulent fields, the scalar field, in all cases, is unchanged by these. The mixing dynamics in the scalar field are found to be insensitive to the source of turbulent kinetic energy production (non-buoyant vs. buoyant).