Investigations in flow injection analysis (FIA): conventional FIA determination of chloride in water; sequential injection (SI)-FIA determination of mercury in water

Flow injection analysis (FIA) was applied to the determination of both chloride ion and mercury in water. Conventional FIA was employed for the chloride study. Investigations of the Fe3 +/Hg(SCN)2/CI-,450 nm spectrophotometric system for chloride determination led to the discovery of an absorbance in the 250-260 nm region when Hg(SCN)2 and CI- are combined in solution, in the absence of iron(III). Employing an in-house FIA system, absorbance observed at 254 nm exhibited a linear relation from essentially 0 - 2000 Jlg ml- 1 injected chloride. This linear range spanning three orders of magnitude is superior to the Fe3+/Hg(SCN)2/CI- system currently employed by laboratories worldwide. The detection limit obtainable with the proposed method was determin~d to be 0.16 Jlg ml- 1 and the relative standard deviation was determined to be 3.5 % over the concentration range of 0-200 Jig ml- 1. Other halogen ions were found to interfere with chloride determination at 254 nm whereas cations did not interfere. This system was successfully applied to the determination of chloride ion in laboratory water. Sequential injection (SI)-FIA was employed for mercury determination in water with the PSA Galahad mercury amalgamation, and Merlin mercury fluorescence detection systems. Initial mercury in air determinations involved injections of mercury saturated air directly into the Galahad whereas mercury in water determinations involved solution delivery via peristaltic pump to a gas/liquid separator, after reduction by stannous chloride. A series of changes were made to the internal hardware and valving systems of the Galahad mercury preconcentrator. Sequential injection solution delivery replaced the continuous peristaltic pump system and computer control was implemented to control and integrate all aspects of solution delivery, sample preconcentration and signal processing. Detection limits currently obtainable with this system are 0.1 ng ml-1 HgO.

Phytoplankton species diversity of 27 lakes and ponds of Costa Rica (Central America)

The literature on species diversity of phytoplankton of tropical lakes is scarce, and for the main part comes from studies of the big lakes in Africa, or deep lakes in South America, leaving a gap in the information about small shallow tropical lakes. In the present work the phytoplankton species composition and diversity of 27 shallow lakes and ponds in Costa Rica (Central America) was studied. The species composition was found to agree with other studies of tropical lakes, with a dominance of Chlorophyta, Cyanophyta, or in some cases Bacillariophyta or Euglenophyta; and a general paucity of Chrysophyta and Cryptophyta. Species richness varied considerably among the lakes, and tended to decrease with an increase in lake elevation. A low evenness in the species abundances was found, with one or more species outnumbering the rest by several orders of magnitude. Individual species abundances and species composition was found to vary with time in Rio Cuarto Lake, a meromictic lake situated in a region with low seasonal change in precipitation. In comparison with the phytoplankton of temperate lakes, the phytoplankton of the tropical lakes studied tended to have a lower evenness of species abundances, although species richness may be similar to temperate figures in some cases. Diversity indices sensitive to changes in the abundance of rare species tend to be higher in the tropical lakes studied; diversity indices sensitive to changes in the numbers of abundant species tend to be similar between the temperate and tropical lakes examined.

Role of Nuclear Angiotensin-II Receptor Mediated Signalling in Cardiovascular Remodelling

Le remodelage cardiaque est le processus par lequel la structure ou la fonction cardiaque change en réponse à un déséquilibre pathophysiologique tel qu'une maladie cardiaque, un contexte d'arythmie prolongée ou une modification de l'équilibre hormonal. Le système rénine-angiotensine (SRA) est un système hormonal largement étudié et il est impliqué dans de nombreuses activités associées au remodelage cardiovasculaire. L’existence d'un système circulatoire couplé à un système de tissus locaux est une représentation classique, cependant de nouvelles données suggèrent un SRA indépendant et fonctionnellement actif à l'échelle cellulaire. La compréhension de l'activité intracellulaire du SRA pourrait mener à de nouvelles pistes thérapeutiques qui pourraient prévenir un remodelage cardiovasculaire défavorable. L'objectif de cette thèse était d'élucider le rôle du SRA intracellulaire dans les cellules cardiaques. Récemment, les récepteurs couplés aux protéines G (RCPG), les protéines G et leurs effecteurs ont été détectés sur des membranes intracellulaires, y compris sur la membrane nucléaire, et les concepts de RCPG intracellulaires fonctionnels sont en voie d'être acceptés comme une réalité. Nous avons dès lors fait l'hypothèse que la signalisation du SRA délimitant le noyau était impliquée dans le contrôle de l'expression des gènes cardiaques. Nous avons démontré la présence de récepteurs d'angiotensine de type-1 (AT1R) et de type-2 (AT2R) nucléaires dans les cardiomyocytes ventriculaires adultes et dans une fraction nucléaire purifiée de tissu cardiaque. Des quantités d'Ang II ont été détectées dans du lysat de cardiomyocytes et des microinjections d'Ang-II-FITC ont donné lieu à des liaisons préférentielles aux sites nucléaires. L'analyse transcriptionnelle prouve que la synthèse d'ARN de novo dans des noyaux isolés stimulés à l'Ang-II, et l'expression des ARNm de NF-κB étaient beaucoup plus importants lorsque les noyaux étaient exposés à de l'Ang II par rapport aux cardiomyocytes intacts. La stimulation des AT1R nucléaires a engendré une mobilisation de Ca2+ via les récepteurs de l'inositol trisphosphate (IP3R), et le blocage des IP3R a diminué la réponse transcriptionnelle. Les méthodes disponibles actuellement pour l'étude de la signalisation intracrine sont limitées aux méthodes indirectes. L'un des objectifs de cette thèse était de synthétiser et caractériser des analogues d'Ang-II cellule-perméants afin d’étudier spécifiquement dans les cellules intactes l'activité intracellulaire du SRA. Nous avons synthétisé et caractérisé pharmacologiquement des analogues photosensibles Ang-II encapsulée en incorporant un groupement 4,5-diméthoxy-2-nitrobenzyl (DMNB) photoclivable sur les sites actifs identifiés du peptide. Chacun des trois analogues d'Ang II encapsulée synthétisés et purifiés: [Tyr(DMNB)4]Ang-II, Ang-II-ODMNB et [Tyr(DMNB)4]Ang-II-ODMNB a montré une réduction par un facteur deux ou trois de l'affinité de liaison envers AT1R et AT2R dans les dosages par liaison compétitive et une activité réduite dans la contraction de l'aorte thoracique. La photostimulation de [Tyr(DMNB)4]Ang-II dans des cellules HEK a augmenté la phosphorylation d'ERK1/2 (via AT1R) et la production de cGMP (via AT2R) alors que dans les cardiomyocytes isolés elle générait une augmentation de Ca2+ nucléoplasmique et initiait la synthèse d'ARNr 18S et d'ARNm du NF-κB. Les fibroblastes sont les principaux générateurs de remodelage cardiaque structurel, et les fibroblastes auriculaires sont plus réactifs aux stimuli profibrotiques que les fibroblastes ventriculaires. Nous avons émis l'hypothèse que l’Ang-II intracellulaire et l'activation des AT1R et AT2R nucléaires associés contrôlaient les profils d'expression des gènes des fibroblastes via des systèmes de signalisation distincts et de ce fait jouaient un rôle majeur dans le développement de la fibrose cardiaque. Nous avons remarqué que les fibroblastes auriculaires expriment l’AT1R et l’AT2R nucléaire et l'Ang-II au niveau intracellulaire. L’expression d'AT1R nucléaire a été régulés positivement dans les cas d’insuffisance cardiaque (IC), tandis que l'AT2R nucléaire a été glycosylé post-traductionnellement. La machinerie protéique des protéines G, y compris Gαq/11, Gαi/3, et Gβ, a été observée dans des noyaux isolés de fibroblastes. AT1R et AT2R régulent l'initiation de la transcription du fibroblaste via les voies de transduction de signal d'IP3R et du NO. La photostimulation de [Tyr(DMNB)4]Ang-II dans une culture de fibroblastes auriculaire déclenche la libération de Ca2+ nucléoplasmique, la prolifération, et la synthèse et sécrétion de collagène qui ne sont pas inhibées par les bloqueurs d'AT1R et/ou AT2R extracellulaires.

Theory of Breaking of a Potyrner Molecule under Tension

The thesis presents the dynamics of a polymer chain under tension. It includes existing theories of polymer fracture, important theories of reaction rates, the rate using multidimensional transition state theory and apply it to the case of polyethylene etc. The main findings of the study are; the life time of the bond is somewhat sensitive to the potential lead to rather different answers, for a given potential a rough estimate of the rate can be obtained by a simples approximation that considers the dynamics of only the bond that breaks and neglects the coupling to neighboring bonds. Dynamics of neighboring bonds would decrease the rate, but usually not more than by one order of magnitude, for the breaking of polyethylene, quantum effects are important only for temperatures below 150K, the lifetime strongly depends on the strain and as the strain varies over a narrow range, the life varies rapidly from 105 seconds to 10_5 seconds, if we change one unit of the polymer by a foreign atom, say by one sulphure atom, in the main chain itself, by a weaker bond, the rate is found to increase by orders of magnitude etc.

Ultrasonic measurement of the elastic properties of benzoyl glycine single crystals

Certain organic crystals are found to possess high non- linear optical coefficients,often one to two orders of magnitude higher than those of the well known inorganic non-linear optical materials.Benzoyl glycine is one such crystal whose optical second-harmonic generation efficiency is much higher than that of potassium dihydrogen phosphate. Single crystals of benzoyl glycine are grown by solvent evaporation technique using N,N-dimethyl formamide as the solvent.All the nine second-order elastic stiffness constants of this orthorhombic crystal are determined from ultrasonic wave velocity measurements employing the pulse echo overlap technique.The anisotropy of elastic wave propagation in this crystal is demonstrated by plotting the phase velocity, slowness,Young's modulus and linear compressibility surfaces along symmetry planes.The volume compressibility, bulk modulus and relevant Poisson's ratios are also determined. Variation of the diagonal elastic stiffness constants with temperature over a limited range are measured and reported.

Modelling of Ultraviolet and Vissible Emissions in Comets

Comets are the spectacular objects in the night sky since the dawn of mankind. Due to their giant apparitions and enigmatic behavior, followed by coincidental calamities, they were termed as notorious and called as `bad omens'. With a systematic study of these objects modern scienti c community understood that these objects are part of our solar system. Comets are believed to be remnant bodies of at the end of evolution of solar system and possess the material of solar nebula. Hence, these are considered as most pristine objects which can provide the information about the conditions of solar nebula. These are small bodies of our solar system, with a typical size of about a kilometer to a few tens of kilometers orbiting the Sun in highly elliptical orbits. The solid body of a comet is nucleus which is a conglomerated mixture of water ice, dust and some other gases. When the cometary nucleus advances towards the Sun in its orbit the ices sublimates and produces the gaseous envelope around the nucleus which is called coma. The gravity of cometary nucleus is very small and hence can not in uence the motion of gases in the cometary coma. Though the cometary nucleus is a few kilometers in size they can produce a transient, extensive, and expanding atmosphere with size several orders of magnitude larger in space. By ejecting gas and dust into space comets became the most active members of the solar system. The solar radiation and the solar wind in uences the motion of dust and ions and produces dust and ion tails, respectively. Comets have been observed in di erent spectral regions from rocket, ground and space borne optical instruments. The observed emission intensities are used to quantify the chemical abundances of di erent species in the comets. The study of various physical and chemical processes that govern these emissions is essential before estimating chemical abundances in the coma. Cameron band emission of CO molecule has been used to derive CO2 abundance in the comets based on the assumption that photodissociation of CO2 mainly produces these emissions. Similarly, the atomic oxygen visible emissions have been used to probe H2O in the cometary coma. The observed green ([OI] 5577 A) to red-doublet emission ([OI] 6300 and 6364 A) ratio has been used to con rm H2O as the parent species of these emissions. In this thesis a model is developed to understand the photochemistry of these emissions and applied to several comets. The model calculated emission intensities are compared with the observations done by space borne instruments like International Ultraviolet Explorer (IUE) and Hubble Space Telescope (HST) and also by various ground based telescopes.

Photoionization of Kr near 4s threshold: II. Intermediate-coupling theory

The Kr 4s-electron photoionization cross section as a function of the exciting-photon energy in the range between 30 eV and 90 eV was calculated using the configuration interaction (CI) technique in intermediate coupling. In the calculations the 4p spin-orbital interaction and corrections due to higher orders of perturbation theory (the so-called Coulomb interaction correlational decrease) were considered. Energies of Kr II states were calculated and agree with spectroscopic data within less than 10 meV. For some of the Kr II states new assignments were suggested on the basis of the largest component among the calculated CI wavefunctions.

Solution of the Hartree-Fock-Slater equations for diatomic molecules by the finite-element method

We present the finite-element method in its application to solving quantum-mechanical problems for diatomic molecules. Results for Hartree-Fock calculations of H_2 and Hartree-Fock-Slater calculations for molecules like N_2 and CO are presented. The accuracy achieved with fewer than 5000 grid points for the total energies of these systems is 10^-8 a.u., which is about two orders of magnitude better than the accuracy of any other available method.

First-principles electronic theory of non-collinear magnetic order in transition-metal nanowires

The structural, electronic and magnetic properties of one-dimensional 3d transition-metal (TM) monoatomic chains having linear, zigzag and ladder geometries are investigated in the frame-work of first-principles density-functional theory. The stability of long-range magnetic order along the nanowires is determined by computing the corresponding frozen-magnon dispersion relations as a function of the 'spin-wave' vector q. First, we show that the ground-state magnetic orders of V, Mn and Fe linear chains at the equilibrium interatomic distances are non-collinear (NC) spin-density waves (SDWs) with characteristic equilibrium wave vectors q that depend on the composition and interatomic distance. The electronic and magnetic properties of these novel spin-spiral structures are discussed from a local perspective by analyzing the spin-polarized electronic densities of states, the local magnetic moments and the spin-density distributions for representative values q. Second, we investigate the stability of NC spin arrangements in Fe zigzag chains and ladders. We find that the non-collinear SDWs are remarkably stable in the biatomic chains (square ladder), whereas ferromagnetic order (q =0) dominates in zigzag chains (triangular ladders). The different magnetic structures are interpreted in terms of the corresponding effective exchange interactions J(ij) between the local magnetic moments μ(i) and μ(j) at atoms i and j. The effective couplings are derived by fitting a classical Heisenberg model to the ab initio magnon dispersion relations. In addition they are analyzed in the framework of general magnetic phase diagrams having arbitrary first, second, and third nearest-neighbor (NN) interactions J(ij). The effect of external electric fields (EFs) on the stability of NC magnetic order has been quantified for representative monoatomic free-standing and deposited chains. We find that an external EF, which is applied perpendicular to the chains, favors non-collinear order in V chains, whereas it stabilizes the ferromagnetic (FM) order in Fe chains. Moreover, our calculations reveal a change in the magnetic order of V chains deposited on the Cu(110) surface in the presence of external EFs. In this case the NC spiral order, which was unstable in the absence of EF, becomes the most favorable one when perpendicular fields of the order of 0.1 V/Å are applied. As a final application of the theory we study the magnetic interactions within monoatomic TM chains deposited on graphene sheets. One observes that even weak chain substrate hybridizations can modify the magnetic order. Mn and Fe chains show incommensurable NC spin configurations. Remarkably, V chains show a transition from a spiral magnetic order in the freestanding geometry to FM order when they are deposited on a graphene sheet. Some TM-terminated zigzag graphene-nanoribbons, for example V and Fe terminated nanoribbons, also show NC spin configurations. Finally, the magnetic anisotropy energies (MAEs) of TM chains on graphene are investigated. It is shown that Co and Fe chains exhibit significant MAEs and orbital magnetic moments with in-plane easy magnetization axis. The remarkable changes in the magnetic properties of chains on graphene are correlated to charge transfers from the TMs to NN carbon atoms. Goals and limitations of this study and the resulting perspectives of future investigations are discussed.

Estimates of Avian Mortality Attributed to Vehicle Collisions in Canada

Although mortality of birds from collisions with vehicles is estimated to be in the millions in the USA, Europe, and the UK, to date, no estimates exist for Canada. To address this, we calculated an estimate of annual avian mortality attributed to vehicular collisions during the breeding and fledging season, in Canadian ecozones, by applying North American literature values for avian mortality to Canadian road networks. Because owls are particularly susceptible to collisions with vehicles, we also estimated the number of roadkilled Barn owls (Tyto alba) in its last remaining range within Canada. (This species is on the IUCN red list and is also listed federally as threatened; Committee on the Status of Endangered Wildlife in Canada 2010, International Union for the Conservation of Nature 2012). Through seven Canadian studies in existence, 80 species and 2,834 specimens have been found dead on roads representing species from 14 orders of birds. On Canadian 1 and 2-lane paved roads outside of major urban centers, the unadjusted number of bird mortalities/yr during an estimated 4-mo (122-d) breeding and fledging season for most birds in Canada was 4,650,137 on roads traversing through deciduous, coniferous, cropland, wetlands and nonagricultural landscapes with less than 10% treed area. On average, this represents 1,167 birds killed/100 km in Canada. Adjusted for scavenging, this estimate was 13,810,906 (3,462 dead birds/100 km). For barn owls, the unadjusted number of birds killed annually on 4-lane roads during the breeding and fledging season, within the species geographic range in southern British Columbia, was estimated as 244 owls and, when adjusted for scavenging and observer bias (3.6 factor), the total was 851 owls.

Stratosphere-troposphere transport in a numerical simulation of midlatitude convection

The transport of stratospheric air deep into the troposphere via convection is investigated numerically using the UK Met Office Unified Model. A convective system that formed on 27 June 2004 near southeast England, in the vicinity an upper level potential vorticity anomaly and a lowered tropopause, provides the basis for analysis. Transport is diagnosed using a stratospheric tracer that can either be passed through or withheld from the model’s convective parameterization scheme. Three simulations are performed at increasingly finer resolutions, with horizontal grid lengths of 12, 4, and 1 km. In the 12 and 4 km simulations, tracer is transported deeply into the troposphere by the parameterized convection. In the 1 km simulation, for which the convective parameterization is disengaged, deep transport is still accomplished but with a much smaller magnitude. However, the 1 km simulation resolves stirring along the tropopause that does not exist in the coarser simulations. In all three simulations, the concentration of the deeply transported tracer is small, three orders of magnitude less than that of the shallow transport near the tropopause, most likely because of the efficient dilution of parcels in the lower troposphere.

Variograms of ancillary data to aid sampling for soil surveys

To provide reliable estimates for mapping soil properties for precision agriculture requires intensive sampling and costly laboratory analyses. If the spatial structure of ancillary data, such as yield, digital information from aerial photographs, and soil electrical conductivity (EC) measurements, relates to that of soil properties they could be used to guide the sampling intensity for soil surveys. Variograins of permanent soil properties at two study sites on different parent materials were compared with each other and with those for ancillary data. The ranges of spatial dependence identified by the variograms of both sets of properties are of similar orders of magnitude for each study site, Maps of the ancillary data appear to show similar patterns of variation and these seem to relate to those of the permanent properties of the soil. Correlation analysis has confirmed these relations. Maps of kriged estimates from sub-sampled data and the original variograrns showed that the main patterns of variation were preserved when a sampling interval of less than half the average variogram range of ancillary data was used. Digital data from aerial photographs for different years and EC appear to show a more consistent relation with the soil properties than does yield. Aerial photographs, in particular those of bare soil, seem to be the most useful ancillary data and they are often cheaper to obtain than yield and EC data.

Fast approximate calculation of multiply scattered lidar returns

An efficient method is described for the approximate calculation of the intensity of multiply scattered lidar returns. It divides the outgoing photons into three populations, representing those that have experienced zero, one, and more than one forward-scattering event. Each population is parameterized at each range gate by its total energy, its spatial variance, the variance of photon direction, and the covariance, of photon direction and position. The result is that for an N-point profile the calculation is O(N-2) efficient and implicitly includes up to N-order scattering, making it ideal for use in iterative retrieval algorithms for which speed is crucial. In contrast, models that explicitly consider each scattering order separately are at best O(N-m/m!) efficient for m-order scattering and often cannot be performed to more than the third or fourth order in retrieval algorithms. For typical cloud profiles and a wide range of lidar fields of view, the new algorithm is as accurate as an explicit calculation truncated at the fifth or sixth order but faster by several orders of magnitude. (C) 2006 Optical Society of America.

Extraction of tidal channel networks from airborne scanning laser altimetry and aerial photography

The study of the morphodynamics of tidal channel networks is important because of their role in tidal propagation and the evolution of salt-marshes and tidal flats. Channel dimensions range from tens of metres wide and metres deep near the low water mark to only 20-30cm wide and 20cm deep for the smallest channels on the marshes. The conventional method of measuring the networks is cumbersome, involving manual digitising of aerial photographs. This paper describes a semi-automatic knowledge-based network extraction method that is being implemented to work using airborne scanning laser altimetry (and later aerial photography). The channels exhibit a width variation of several orders of magnitude, making an approach based on multi-scale line detection difficult. The processing therefore uses multi-scale edge detection to detect channel edges, then associates adjacent anti-parallel edges together to form channels using a distance-with-destination transform. Breaks in the networks are repaired by extending channel ends in the direction of their ends to join with nearby channels, using domain knowledge that flow paths should proceed downhill and that any network fragment should be joined to a nearby fragment so as to connect eventually to the open sea.

The income requirements of marine protected areas

Given the growing impact of human activities on the sea, managers are increasingly turning to marine protected areas (MPAs) to protect marine habitats and species. Many MPAs have been unsuccessful, however, and lack of income has been identified as a primary reason for failure. In this study, data from a global survey of 79 MPAs in 36 countries were analysed and attempts made to construct predictive models to determine the income requirements of any given MPA. Statistical tests were used to uncover possible patterns and relationships in the data, with two basic approaches. In the first of these, an attempt was made to build an explanatory "bottom-up" model of the cost structures that might be required to pursue various management activities. This proved difficult in practice owing to the very broad range of applicable data, spanning many orders of magnitude. In the second approach, a "top-down" regression model was constructed using logarithms of the base data, in order to address the breadth of the data ranges. This approach suggested that MPA size and visitor numbers together explained 46% of the minimum income requirements (P < 0.001), with area being the slightly more influential factor. The significance of area to income requirements was of little surprise, given its profile in the literature. However, the relationship between visitors and income requirements might go some way to explaining why northern hemisphere MPAs with apparently high incomes still claim to be under-funded. The relationship between running costs and visitor numbers has important implications not only in determining a realistic level of funding for MPAs, but also in assessing from where funding might be obtained. Since a substantial proportion of the income of many MPAs appears to be utilized for amenity purposes, a case may be made for funds to be provided from the typically better resourced government social and educational budgets as well as environmental budgets. Similarly visitor fees, already an important source of funding for some MPAs, might have a broader role to play in how MPAs are financed in the future. (C) 2007 Elsevier Ltd. All rights reserved.