Ecological significance of seasonal variation in clutch-size of Arctodiaptomus bacillifer in alpine lakes of high altitudes (Val Bognanco) [Translation from: Bollettino di Zoologia 37 491-492, 1970]

This brief paper describes the significance of seasonal variation in clutch-size of the copepod Arctodiaptomus bacillifer in alpine lakes of high altitudes (Val Bognanco). Seasonal dynamics of the zooplankton of these lakes was studied during summer and autumn of 1968 and 1969and results are summarised.

Mellum Island (southern North Sea): dynamic processes and sedimentary structures. I. Southern tidal flat, transition zone and high-surface.[p.72 (Blasensand) only][Translation from: Senckenbergiana Maritima 11, 59-113, 1979]

This partial translation of a longer article describes the phenomenon of ”Blasensand”. Blasensand is formed when sedimentation of dried out sand is suddenly flooded from above. A more detailed explanation of Blasensand is given in this translated part of the paper.

Ecological study of the River Lambourn. Report for the period October 1970 to March 1972

A small investigation of the ecology of the river Lambourn was carried out during 1967-70. During this period it became clear that detailed and reliable information could only be obtained by a much larger investigation. The present study was planned to meet the minimum requirements. No pumping is expected during this period and, since the pumping carried out during the pilot scheme was on a small scale, it is reasonable to assume that the river is still relatively unaffected by pumping.The present investigation has two main objectives both of which depend on obtaining a detailed picture of the ecology of the river at the present time. First, it will provide basic information on the state of the river prior to the development of the pumping scheme which will be available for comparison at any later date. Secondly, it may be possible to use some of the data to predict the ecological changes which may occur if the flow of the river is altered by the pumping scheme. This report is part of a series of fives studies on the River Lambourn which were undertaken between 1970 and 1979. [PDF contains 83 pages]

Ecological study of the River Lambourn. Report for the period October 1970 to September 1973

Few detailed studies have been made on the ecology of the chalk streams. A complex community of plants and animals is present and much more information is required to achieve an understanding of the requirements and interactions of all the species. It is important that the rivers affected by this scheme should be studied and kept under continued observation so that any effects produced by the scheme can be detected. This need has been recognised by the Thames Conservancy and the Water Resources Board who jointly sponsored this investigation on one of the chalk streams involved in the scheme. The present investigation has two main objectives both of which depend on obtaining a detailed picture of the ecology of the river at the present time. First, it will provide basic information on the state of the river prior to the development of the pumping scheme which will be available for comparison at any later date. Secondly, it may be possible to use some of the data to predict the ecological changes which may occur if the flow of the river is altered by the pumping scheme. The study covers suspended solids, invertebrates, fish.This report is part of a series of fives studies on the River Lambourn which were undertaken between 1970 and 1979. [PDF contains 24 pages]

Ecological study of chalk and limestone streams. Annual Report October 1974 to September 1975

Few detailed studies have been made on the ecology of the chalk streams. A complex community of plants and animals is present and much more information is required to achieve an understanding of the requirements and interactions of all the species. It is important that the rivers affected by this scheme should be studied and kept under continued observation so that any effects produced by the scheme can be detected. The report gives a brief synopsis of work carried out during the second year of a four year ecological study sponsored jointly by the Thames Water Authority and the Central Water Planning Unit. It assumes some familiarity with the investigations carried out on the River Lambourn during the preceding three years which was sponsored jointly by the Thames Conservancy and Water Resources Board (immediate predecessors of the present sponsoring organisations). (PDF contains 31 pages)

Ecological study of chalk and limestone stream. Annual report October 1975 to September 1976

Few detailed studies have been made on the ecology of the chalk streams. A complex community of plants and animals is present and much more information is required to achieve an understanding of the requirements and interactions of all the species. It is important that the rivers affected by this scheme should be studied and kept under continued observation so that any effects produced by the scheme can be detected. The report gives a brief synopsis of work carried out during the third year of a four year ecological study sponsored jointly by the Thames Water Authority and the Central Water Planning Unit. It assumes . It assumes some familiarity with the investigations carried out on the River Lambourn during the preceding three years which was sponsored jointly by the Thames Conservancy and Water Resources Board (immediate predecessors of the present sponsoring organisations). (PDF contains 35 pages)

Ecological study of chalk streams. Lambourn project. Interim report October 1977 to April 1979

Few detailed studies have been made on the ecology of the chalk streams. A complex community of plants and animals is present and much more information is required to achieve an understanding of the requirements and interactions of all the species. It is important that the rivers affected by this scheme should be studied and kept under continued observation so that any effects produced by the scheme can be detected. The report gives a synopsis of work carried out between 1971 and 1979 focusing on the present phase 1978-1979. It assumes some familiarity with the investigations carried out on the River Lambourn during the preceding years. The aims of the present phase of the project may be divided into two broad aspects. The first involves collecting further information in the field and includes three objectives: a continuation of studies on the Lambourn sites at Bagnor; comparative studies on other chalk streams; and a comparative study on a limestone stream. The second involves detailed analyses of data previously collected to document the recovery of the Lambourn from operational pumping and to attempt to develop simple conceptual and predictive models applicable over a wide range of physical and geographical variables. (PDF contains 43 pages)

Ecological study of the River Lambourn. Report for the period October 1973 to September 1977

The investigations described in this report were carried out to fulfill three distinct but interrelated objectives. In 1973 the Thames Conservancy were making plans for a second stage of their groundwater scheme which would take water from the chalk aquifers in the valley of the Kennet and they wanted basic information on the ecological state of this river and its upper tributaries. Little appeared to be known about limestone streams and a preliminary study of one of the streams in this area was desirable as a basis for planning more detailed studies if these were needed later. At a progress meeting held in March 1976 the problems and opportunities presented by the developing drought conditions were considered. It was concluded that the ecological effects of the exceptionally low natural flows should be studied and that it would be important to assess the ecological impact of the groundwater scheme if it was brought into operation that year. This could only be done on the Lambourn and the Winterbourne and it was decided that considerable effort should be diverted there for this purpose and that the field observations should be extended to cover any recovery period after the end of the drought. To make this possible it was agreed that the studies of invertebrates and detritus on the Kennet should be reduced considerably and that the proposed study of the limestone stream should be abandoned. The revised objectives were as follows: A detailed ecological study of several sites on the Kennet and its tributaries above Kintbury, extending over at least two years and involving observations on wate r weeds , invertebrates, fish, detritus and the trophic relationships within the river community. Quantitativ e and qualitative sampling of water weeds and invertebrates during one year at a number of sites on several chalk streams to determine whether the patterns and relationships found in the Lambourn are also found at the other sites. Observations on the Lambourn at Bagnor were to continue for most of the period to look for long-term fluctuations and to enable these sites to act as controls with which the other sites could be compared. Further detailed studies on the Lambourn and the Winterbourne to assess the impact of low flows, trial pumping and the operation of the groundwater scheme.

Ecological effects of trial pumpings in the Upper Lambourn: Stage 1 group pumping test Upper Lambourn group, September - November 1975

This report to the Thames Water Authority and Central Water Planning Unit is on research carried out in conjunction with the Stage 1 Group Pumping Test of five boreholes in the upper Lambourn Group for a period of three months in September, October and November 1975. The aim of the study was to assess the ecological effects of the pumpin g of five bore-holes in the upper Lambourn. That is, to determine how the seasonal sequence of ecological events in the river differed from what would hav e occurred had no pumping taken place. Since this 'experiment' has no control it is not possible to make a direct assessment. Nevertheless, by careful monitoring of ecological events before, during and after the pumping it is possible to document changes in th e river and by reference to the data already available for the Rive r Lambourn, normal seasonal changes in the flora and fauna can be separated from changes which may be attributable to the pumping and subsequent events.

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.

The Design and Synthesis of Transition Metal Complexes Supported by Non-innocent Ligand Scaffolds for Small Molecule Activation

This dissertation focuses on the incorporation of non-innocent or multifunctional moieties into different ligand scaffolds to support one or multiple metal centers in close proximity. Chapter 2 focuses on the initial efforts to synthesize hetero- or homometallic tri- or dinuclear metal carbonyl complexes supported by para-terphenyl diphosphine ligands. A series of [M₂M’(CO)₄]-type clusters (M = Ni, Pd; M’ = Fe, Co) could be accessed and used to relate the metal composition to the properties of the complexes. During these studies it was also found that non-innocent behavior was observed in dinuclear Fe complexes that result from changes in oxidation state of the cluster. These studies led to efforts to rationally incorporate central arene moieties capable managing both protons and electrons during small molecule activation.

Chapter 3 discusses the synthesis of metal complexes supported by a novel para-terphenyl diphosphine ligand containing a non-innocent 1,4-hydroquinone moiety as the central arene. A Pd⁰-hydroquinone complex was found to mediate the activation of a variety of small molecules to form the corresponding Pd⁰-quinone complexes in a formal two proton ⁄ two electron transformation. Mechanistic investigations of dioxygen activation revealed a metal-first activation process followed by subsequent proton and electron transfer from the ligand. These studies revealed the capacity of the central arene substituent to serve as a reservoir for a formal equivalent of dihydrogen, although the stability of the M-quinone compounds prevented access to the PdII-quinone oxidation state, thus hindering of small molecule transformations requiring more than two electrons per equivalent of metal complex.

Chapter 4 discusses the synthesis of metal complexes supported by a ligand containing a 3,5-substituted pyridine moiety as the linker separating the phenylene phosphine donors. Nickel and palladium complexes supported by this ligand were found to tolerate a wide variety of pyridine nitrogen-coordinated electrophiles which were found to alter central pyridine electronics, and therefore metal-pyridine π-system interactions, substantially. Furthermore, nickel complexes supported by this ligand were found to activate H-B and H-Si bonds and formally hydroborate and hydrosilylate the central pyridine ring. These systems highlight the potential use of pyridine π-system-coordinated metal complexes to reversibly store reducing equivalents within the ligand framework in a manner akin to the previously discussed 1,4-hydroquinone diphosphine ligand scaffold.

Chapter 5 departs from the phosphine-based chemistry and instead focuses on the incorporation of hydrogen bonding networks into the secondary coordination sphere of [Fe₄(μ₄-O)]-type clusters supported by various pyrazolate ligands. The aim of this project is to stabilize reactive oxygenic species, such as oxos, to study their spectroscopy and reactivity in the context of complicated multimetallic clusters. Herein is reported this synthesis and electrochemical and Mössbauer characterization of a series of chloride clusters have been synthesized using parent pyrazolate and a 3-aminophenyl substituted pyrazolate ligand. Efforts to rationally access hydroxo and oxo clusters from these chloride precursors represents ongoing work that will continue in the group.

Appendix A discusses attempts to access [Fe₃Ni]-type clusters as models of the enzymatic active site of [NiFe] carbon monoxide dehydrogenase. Efforts to construct tetranuclear clusters with an interstitial sulfide proved unsuccessful, although a (μ₃-S) ligand could be installed through non-oxidative routes into triiron clusters. While [Fe₃Ni(μ₄-O)]-type clusters could be assembled, accessing an open heterobimetallic edge site proved challenging, thus prohibiting efforts to study chemical transformations, such as hydroxide attack onto carbon monoxide or carbon dioxide coordination, relevant to the native enzyme. Appendix B discusses the attempts to synthesize models of the full H-cluster of [FeFe]-hydrogenase using a bioinorganic approach. A synthetic peptide containing three cysteine donors was successfully synthesized and found to chelate a preformed synthetic [Fe₄S₄] cluster. However, efforts to incorporate the diiron subsite model complex proved challenging as the planned thioester exchange reaction was found to non-selectively acetylate the peptide backbone, thus preventing the construction of the full six-iron cluster.

Ecological indicators of water quality in small rivers

At the present time hydrobiological indicators are widely used for the control of surface water quality. Results of the applying of methods suggested at the 1st Soviet-American seminar (1975), development of improved methods and estimation of their usefulness for various conditions are presented in this report. Among the criteria permitting an estimation of the degree and character of changes in water quality and their connection with the functioning of river ecosystems in general, the biological tests of natural waters appears to be the most universal one and is being carried out in two main directions — ecological and physiological. This study summarises approaches in both directions.

I. Baryon-antibaryon phase transition at high temperature. II. Inclusive virtual photon-hadron reactions in the parton model

Part I

Present experimental data on nucleon-antinucleon scattering allow a study of the possibility of a phase transition in a nucleon-antinucleon gas at high temperature. Estimates can be made of the general behavior of the elastic phase shifts without resorting to theoretical derivation. A phase transition which separates nucleons from antinucleons is found at about 280 MeV in the approximation of the second virial coefficient to the free energy of the gas.

Part II

The parton model is used to derive scaling laws for the hadrons observed in deep inelastic electron-nucleon scattering which lie in the fragmentation region of the virtual photon. Scaling relations are obtained in the Bjorken and Regge regions. It is proposed that the distribution functions become independent of both q² and ν where the Bjorken and Regge regions overlap. The quark density functions are discussed in the limit x→1 for the nucleon octet and the pseudoscalar mesons. Under certain plausible assumptions it is found that only one or two quarks of the six types of quarks and antiquarks have an appreciable density function in the limit x→1. This has implications for the quark fragmentation functions near the large momentum boundary of their fragmentation region. These results are used to propose a method of measuring the proton and neutron quark density functions for all x by making measurements on inclusively produced hadrons in electroproduction only. Implications are also discussed for the hadrons produced in electron-positron annihilation.

1. Ultrasonic studies of binary liquid structure in the critical region. Theory and experiment for the 2,6-lutidine/water system. 2. Hartree-Fock calculations of electric polarizabilities of some simple atoms and molecules, and their practicality. 3. Calculation of vibrational transition probabilities in collinear atom-diatom and diatom-diatom collisions with Lennard-Jones interaction

Part 1. Many interesting visual and mechanical phenomena occur in the critical region of fluids, both for the gas-liquid and liquid-liquid transitions. The precise thermodynamic and transport behavior here has some broad consequences for the molecular theory of liquids. Previous studies in this laboratory on a liquid-liquid critical mixture via ultrasonics supported a basically classical analysis of fluid behavior by M. Fixman (e. g., the free energy is assumed analytic in intensive variables in the thermodynamics)--at least when the fluid is not too close to critical. A breakdown in classical concepts is evidenced close to critical, in some well-defined ways. We have studied herein a liquid-liquid critical system of complementary nature (possessing a lower critical mixing or consolute temperature) to all previous mixtures, to look for new qualitative critical behavior. We did not find such new behavior in the ultrasonic absorption ascribable to the critical fluctuations, but we did find extra absorption due to chemical processes (yet these are related to the mixing behavior generating the lower consolute point). We rederived, corrected, and extended Fixman's analysis to interpret our experimental results in these more complex circumstances. The entire account of theory and experiment is prefaced by an extensive introduction recounting the general status of liquid state theory. The introduction provides a context for our present work, and also points out problems deserving attention. Interest in these problems was stimulated by this work but also by work in Part 3.

Part 2. Among variational theories of electronic structure, the Hartree-Fock theory has proved particularly valuable for a practical understanding of such properties as chemical binding, electric multipole moments, and X-ray scattering intensity. It also provides the most tractable method of calculating first-order properties under external or internal one-electron perturbations, either developed explicitly in orders of perturbation theory or in the fully self-consistent method. The accuracy and consistency of first-order properties are poorer than those of zero-order properties, but this is most often due to the use of explicit approximations in solving the perturbed equations, or to inadequacy of the variational basis in size or composition. We have calculated the electric polarizabilities of H₂, He, Li, Be, LiH, and N₂ by Hartree-Fock theory, using exact perturbation theory or the fully self-consistent method, as dictated by convenience. By careful studies on total basis set composition, we obtained good approximations to limiting Hartree-Fock values of polarizabilities with bases of reasonable size. The values for all species, and for each direction in the molecular cases, are within 8% of experiment, or of best theoretical values in the absence of the former. Our results support the use of unadorned Hartree-Pock theory for static polarizabilities needed in interpreting electron-molecule scattering data, collision-induced light scattering experiments, and other phenomena involving experimentally inaccessible polarizabilities.

Part 3. Numerical integration of the close-coupled scattering equations has been carried out to obtain vibrational transition probabilities for some models of the electronically adiabatic H₂-H₂ collision. All the models use a Lennard-Jones interaction potential between nearest atoms in the collision partners. We have analyzed the results for some insight into the vibrational excitation process in its dependence on the energy of collision, the nature of the vibrational binding potential, and other factors. We conclude also that replacement of earlier, simpler models of the interaction potential by the Lennard-Jones form adds very little realism for all the complication it introduces. A brief introduction precedes the presentation of our work and places it in the context of attempts to understand the collisional activation process in chemical reactions as well as some other chemical dynamics.

The ecological impact of different mechanisms of chronic sub-lethal toxicity on feeding and respiratory physiology

Sub-lethal toxicity tests, such as the scope-for-growth test, reveal simple relationships between measures of contaminant concentration and effect on respiratory and feeding physiology. Simple models are presented to investigate the potential impact of different mechanisms of chronic sub-lethal toxicity on these physiological processes. Since environmental quality is variable, even in unimpacted environments, toxicants may have differentially greater impacts in poor compared to higher quality environments. The models illustrate the implications of different degrees and mechanisms of toxicity in response to variability in the quality of the feeding environment, and variability in standard metabolic rate. The models suggest that the relationships between measured degrees of toxic stress, and the maintenance ration required to maintain zero scope-for-growth, may be highly nonlinear. In addition it may be possible to define critical levels of sub-lethal toxic effect above which no environment is of sufficient quality to permit prolonged survival.