Geology of the Rankin Inlet area, Northwest Territories /

The Rankin Inlet area, on the west shore of Hudson Bay in the Northwest Territories, is in the Churchill Structural Province. Metamorphosed volcanic and sedimentary rocks, previously mapped as Archean and part of the Kaminak Group, underlie most of the area. The Rankin Inlet Group consists of greywacke, with minor conglomeratic greywacke, quartzite and dolomite, overlain by massive and pillowed basaltic flows. Gabbro sills intrude the sediments near the base of the volcanic sequence and three serpentinite sills outcrop at the base of the volcanic sequence. The sediments are in fault-contact with quartz monzonite to the south and were intruded by granitic rocks to the northwest. Two periods of folding were defined by the mapping. The first generation folds are recumbent isoclinal folds, with northwest-trending and northeast-dipping axial planes, formed through gravitational sliding. The second generation folds are symmetrically disposed about the axis of the granitic intrusion and have east-southeast trending and nearly vertical axial planes. Whole-rock analysis of 64 rock samples indicates that metasomatic alteration accompanied the intrusion of both the granitic rocks and the serpentinite. The volcanic rocks, gabbro and serpentinite were derived from a magma of oceanic tholeiitic affinities. The stratigraphic sequence and chemistry of the volcanic rocks of the Rankin Inlet Group indicate that this assemblage is correlative with the Hurwitz Group rather than the Kaminak Group and is therefore Aphebian in age.

Ligand Design for Dual Property Single Molecule Magnets

This thesis describes two different approaches for the preparation of polynuclear clusters with interesting structural, magnetic and optical properties. Firstly, exploiting p-tert-butylcalix[4]arene (TBC4) macrocycles together with selected Ln(III) ions for the assembly of emissive single molecule magnets, and secondly the preparation and coordination of a chiral mpmH ligand with selected 3d transition metal ions, working towards the discovery of chiral polynuclear clusters. In Project 1, the coordination chemistry of the TBC4 macrocycle together with Dy(III) and Tb(III) afforded two Ln6[TBC4]2 complexes that have been structurally, magnetically and optically characterized. X-ray diffraction studies reveal that both complexes contain an octahedral core of Ln6 ions capped by two fully deprotonated TBC4 macrocycles. Although the unit cells of the two complexes are very similar, the coordination geometries of their Ln(III) ions are subtly different. Variable temperature ac magnetic susceptibility studies reveal that both complexes display single molecule magnet (SMM) behaviour in zero dc field and the energy barriers and associated pre-exponential factors for each relaxation process have been determined. Low temperature solid state photoluminescence studies reveal that both complexes are emissive; however, the f-f transitions within the Dy6 complex were masked by broad emissions from the TBC4 ligand. In contrast, the Tb(III) complex displayed green emission with the spectrum comprising four sharp bands corresponding to 5D4 → 7FJ transitions (where J = 3, 4, 5 and 6), highlighting that energy transfer from the TBC4 macrocycle to the Tb(III) ion is more effective than to Dy. Examples of zero field Tb(III) SMMs are scarce in the chemical literature and the Tb6[TBC4]2 complex represents the first example of a Tb(III) dual property SMM assembled from a p-tert-butylcalix[4]arene macrocycle with two magnetically derived energy barriers, Ueff of 79 and 63 K. In Project 2, the coordination of both enantiomers of the chiral ligand, α-methyl-2-pyridinemethanol (mpmH) to Ni(II) and Co(II) afforded three polynuclear clusters that have been structurally and magnetically characterized. The first complex, a Ni4 cluster of stoichiometry [Ni4(O2CCMe3)4(mpm)4]·H2O crystallizes in a distorted cubane topology that is well known in Ni(II) cluster chemistry. The final two Co(II) complexes crystallize as a linear mixed valence trimer with stoichiometry [Co3(mpm)6]·(ClO4)2, and a Co4 mixed valence complex [Co(II)¬2Co(III)2(NO3)2(μ-mpm)4(ONO2)2], whose structural topology resembles that of a defective double cubane. All three complexes crystallize in chiral space groups and circular dichroism experiments further confirm that the chirality of the ligand has been transferred to the respective coordination complex. Magnetic susceptibility studies reveal that for all three complexes, there are competing ferro- and antiferromagnetic exchange interactions. The [Co(II)¬2Co(III)2(NO3)2(μ-mpm)4(ONO2)2] complex represents the first example of a chiral mixed valence Co4 cluster with a defective double cubane topology.

Ions of the superheavy elements in vacuum and in solution

The extension of the Periodic Table into the range of unknown atomic numbers of above one hundred requires relativistic calculations. The results of the latter are used to indicate probable values for X-ray transition lines which will be useful for identification of the atomic species formed during collision between accelerated ions and the target. If the half-lives of the isotopes are long, then the chemistry of these new species becomes an important question which is reviewed for E110, E 111 and E112. The possible structural chemistry of the elements E108 to E112 is suggested. Finally the effects of solvation on ions of the actinide and superheavy elements have been studied.

Synthesis of unusual alpha-amino acids and study of the effect of their incorporation into antimicrobial peptides. Total synthesis of biactive marine natural products and analogues thereof

The principle theme of this thesis was the synthesis of bioactive compounds. To this end, this work was focus on two main projects. The first one, which was carried out in the Department of Chemistry of the University of Girona under the supervision of Dr Montserrat Heras, concerned the synthesis of new unnatural amino acids bearing a pyrimidine ring within their side chain for incorporation into the antimicrobial peptide BP100 following a rational design in order to improve its biological profile. On the other hand, the second chapter of this thesis was developed in collaboration with the Laboratoire de Chimie Organique (ESPCI-ParisTech, Paris, France) under the guidance of Pr Janine Cossy and Dr Arseniyadis. This chapter was centered on the total synthesis of three marine natural products with complex structures and interesting biological activities: acremolide B, (–) bitungolide F and lyngbouilloside.

The water quality of the LOCAR Pang and Lambourn catchments

The water quality of the Pang and Lambourn, tributaries of the River Thames, in south-eastern England, is described in relation to spatial and temporal dimensions. The river waters are supplied mainly from Chalk-fed aquifer sources and are, therefore, of a calcium-bicarbonate type. The major, minor and trace element chemistry of the rivers is controlled by a combination of atmospheric and pollutant inputs from agriculture and sewage sources superimposed on a background water quality signal linked to geological sources. Water quality does not vary greatly over time or space. However. in detail, there are differences in water quality between the Pang and Lambourn and between sites along the Pang and the Lambourn. These differences reflect hydrological processes, water flow pathways and water quality input fluxes. The Pangs pattern of water quality change is more variable than that of the Lambourn. The flow hydrograph also shows both a cyclical and 'uniform pattern' characteristic of aquifer drainage with, superimposed, a series of 'flashier' spiked responses characteristic of karstic systems. The Lambourn, in contrast, shows simpler features without the 'flashier' responses, The results are discussed in relation to the newly developed UK community programme LOCAR dealing with Lowland Catchment Research. A descriptive and box model structure is provided to describe the key features of water quality variations in relation to soil, unsaturated and groundwater flows and storage both away from and close to the river.

Kinetic studies of reactions of the nitrate radical (NO3) with peroxy radicals (RO2): an indirect source of OH at night?

A discharge-flow system, coupled to cavity-enhanced absorption spectroscopy (CEAS) detection systems for NO3 at lambda = 662 nm and NO2 at lambda = 404 nm, was used to investigate the kinetics of the reactions of NO3 with eight peroxy radicals at P similar to 5 Torr and T similar to 295 K. Values of the rate constants obtained were (k/10(-12) cm(3) molecule(-1) s(-1)): CH3O2 (1.1 +/- 0.5), C2H5O2 (2.3 +/- 0.7), CH2FO2 (1.4 +/- 0.9), CH2ClO2 (3.8(-2.6)(+1.4)), c-C5H9O2 (1.2(-0.5)(+1.1)), c-C6H11O2 (1.9 +/- 0.7), CF3O2 (0.62 +/- 0.17) and CF3CFO2CF3 (0.24 +/- 0.13). We explore possible relationships between k and the orbital energies of the reactants. We also provide a brief discussion of the potential impact of the reactions of NO3 with RO2 on the chemistry of the night-time atmosphere.

Analyzing Ru(III)-dmso and Ru(III)-dms motifs in compounds used in the synthesis of the antimetastatic agents

The chemistry of Ru(III) complexes containing dmso as a ligand has become an interesting area in the cancer treatment field. Because of this, structural knowledge and chemistry of the moiety Ru(III)-dmso have become important to cancer research. The crystal structures of the compounds mer-[RuCl(3)(dms)(3)] (1) and mer-[RuCl(3)(dms)(2)(dmso)]:mer-[RuCl(3)(dms)(3)] (2) were determined by X-ray crystallography and a speciation of the presence of intramolecular hydrogen bond in these structures has been studied. Compound (1) crystallizes in the orthorhombic space group, Pna2(1); a = 16.591(8) angstrom, b = 8.724(2) angstrom. c = 10.547(3) angstrom; Z = 12 and (2) crystallizes in the space group, P2(1)/C: a = 11.9930(2) angstrom, b = 7.9390(2) angstrom, c = 15.8700(3) angstrom, beta = 93.266(1)degrees, Z = 2. From the X-ray structures solved in this work, were possible to suggest an interpretation for the broad lines observed in the EPR spectra of the Ru(III) compounds explored here. Also, the exchange interactions detected by EPR spectroscopy in solid state and in solution, confirm the presence of van der Waals interactions such as C-H center dot center dot center dot Cl in the compounds (1), (2) and (3). The use of techniques such as IR, UV-vis, (1)H NMR and EPR Spectroscopy and Cyclic Voltammetry were applied in this work to analyze the behavior of these metallocompounds. (c) 2008 Elsevier B.V. All rights reserved.

The balloon flights in the tropics of the hibiscus project

HIBISCUS is a project for studying the dynamics, microphysics and chemistry of the Tropical Tropopause Layer based on balloon measurements. Thirteen heavy sondes and 18 short duration balloons of different types have been used for local process studies. Eight superpressure (BP) and 3 Infra Red Montgolfier (MIR) long duration balloons have been flown for extending the investigations at global scale around the world. Overall the campaign has been very successful operationally as well as scientifically. The paper provides a description of the balloons, the instruments and the strategy used for meeting at best the goals of the project.

ECLAC Development of official statistics in the region. Report of the Economic Commission for Latin America and the Caribbean on the development of official statistics in Latin America and the Caribbean

This document was prepared by the Economic Commission for Latin America and the Caribbean (ECLAC); and offers a description of the main trends in the development of official statistics in Latin America and the Caribbean and the principal challenges in that regard.The first chapter provides an analysis of the state of development of statistical production in the region, based on statistical information for 41 Latin American and Caribbean countries and eight specific areas. The institutional organization of national statistical systems in the region is also described. Chapter II examines the history and current status of mechanisms for regional and subregional coordination and of the Statistical Conference of the Americas of ECLAC. Chapter III describes the main challenges for official statistics in the countries of the region and the strategies that the Statistical Conference of the Americas and ECLAC propose to implement in order to address them.

The Acting in Group of Teachers as Possibility of Resignification of the Interpretation about the Writing Language

Front of the possibility of acting with the teachers who teach in schools of Early Childhood Education for children aged six years, about the re-siginification of the understanding of writing language and of the importance of the child in this age group establish a positive relationship with this mode of language, was developed in 2011, a project linked to the Teaching of UNESP titled “Depathologization learning of the writing and inclusive education: reflections and actions of the teacher of Early Childhood Education”. This project aims to identification of the actions, in the classroom, of the patologization and subsequent implementation of actions depathologization writing by teachers’ actions, considering the increasingly early systematization of formal education of this kind of language in kindergarten. To this end, procedures that characterize the collaborative methodology are adopted. Throughout the methodological course, the engagement of the teachers, of the coordination and of the direction was valued, which seemed to favor both the formation, as the maintenance of the group, were very important aspects to ensure the interaction between its members and the common interest in the reflection about the topic in question. This paper focuses attention on whether thematic axes highlight during the initial survey of the expectations of teachers subsequently addressed in theoretical and reflective meetings leading up to identification of actions the patologization and/or of the proposition of the actions despatologizadoras of the learning of the writing, and in what refers to the way they are addressed.

Impact of the Manaus urban plume on trace gas mixing ratios near the surface in the Amazon Basin: Implications for the NO-NO2-O-3 photostationary state and peroxy radical levels

We measured the mixing ratios of NO, NO2, O-3, and volatile organic carbon as well as the aerosol light-scattering coefficient on a boat platform cruising on rivers downwind of the city of Manaus (Amazonas State, Brazil) in July 2001 (Large-Scale Biosphere-Atmosphere Experiment in Amazonia-Cooperative LBA Airborne Regional Experiment-2001). The dispersion and impact of the Manaus plume was investigated by a combined analysis of ground-based (boat platform) and airborne trace gas and aerosol measurements as well as by meteorological measurements complemented by dispersion calculations (Hybrid Single-Particle Lagrangian Integrated Trajectory model). For the cases with the least anthropogenic influence (including a location in a so far unexplored region similar to 150 km west of Manaus on the Rio Manacapuru), the aerosol scattering coefficient, sigma(s), was below 11 Mm(-1), NOx mixing ratios remained below 0.6 ppb, daytime O-3 mixing ratios were mostly below 20 ppb and maximal isoprene mixing ratios were about 3 ppb in the afternoon. The photostationary state (PSS) was not established for these cases, as indicated by values of the Leighton ratio, Phi, well above unity. Due to the influence of river breeze systems and other thermally driven mesoscale circulations, a change of the synoptic wind direction from east-northeast to south-southeast in the afternoon often caused a substantial increase of ss and trace gas mixing ratios (about threefold for sigma(s), fivefold for NOx, and twofold for O-3), which was associated with the arrival of the Manaus pollution plume at the boat location. The ratio F reached unity within its uncertainty range at NOx mixing ratios of about 3 ppb, indicating "steady-state" conditions in cases when radiation variations, dry deposition, emissions, and reactions mostly involving peroxy radicals (XO2) played a minor role. The median midday/afternoon XO2 mixing ratios estimated using the PSS method range from 90 to 120 parts per trillion (ppt) for the remote cases (sigma(s) < 11 Mm(-1) and NOx < 0.6 ppb), while for the polluted cases our estimates are 15 to 60 ppt. These values are within the range of XO2 estimated by an atmospheric chemistry box model (Chemistry As A Box model Application-Module Efficiently Calculating the Chemistry of the Atmosphere (CAABA/MECCA)-3.0).

Pore-water chemistry of ODP Sites 124-767 and 124-768

The combination of multiple sediment sources and varying rates of sediment accumulation in the Celebes and Sulu seas have had significant impact on the processes of diagenesis, mineralization, and pore-fluid flow. Isotopic and mass-balance calculations help elucidate the various reactions taking place in these western Pacific basins, where ash alteration and basalt-seawater interactions are superimposed on the effects of sulfate oxidation of organic carbon and biogenic methane and of dolomitization of biogenic carbonates. Based on the shape of the calcium and magnesium depth profiles, two major reactive zones have been identified. The first is located near the zone of sulfate depletion and is characterized by carbonate recrystallization, dolomitization and ash alteration reactions at both Ocean Drilling Program Sites 767 and 768. The second reactive zone corresponds to the bottom of the sedimentary sequence and is characterized by alteration reactions in the basement (Site 767) and in the pyroclastic deposits beneath the sediment column (Site 768).

Carbonate composition of Pliocene-Pleistocene sediments of the Maledives

Ocean Drilling Program (ODP) Leg 115 post-cruise research was focused on two Maldives sites, more precisely on the top 108 m of Hole 716B (water depth, 540 m), equivalent to the past 3.5 m.y., and the top 19.5 m of Hole 714A (water depth, 2195 m), equivalent to the past 0.55 m.y. These sediments consist of mostly unaltered and undisturbed, turbidite-free, periplatform ooze. Results of our research are compared with existing data on Hole 633A (water depth, 1681 m), drilled in the Bahamas during ODP Leg 101, using age/depth models built on the basis of oxygen isotope, nannofossil, and magnetic stratigraphies. Climate-induced, long-term (roughly 0.5 m.y.) aragonite cycles, superposed on short-term (roughly 0.04 and 0.1 m.y.) aragonite cycles, have been established at least during the past 2.0 m.y., in the Maldives and the Bahamas. Our most interesting result is the clear correlation among the aragonite long-term cycles in the Maldives and the Bahamas and the carbonate-preservation, long-term cycles from the open Pacific, Indian, and North Atlantic oceans. The mid-Brunhes dissolution interval, corresponding to the youngest preservation minima of the carbonate-preservation, longterm cycles, is clearly defined by fine aragonite minimum values in the deep periplatform sites, and by maximum fragmentation of pteropod tests in the shallow sites. Aragonite and planktonic d18O records, usually in phase during the late Pleistocene, display, further back in time, discreet intervals where the two records do not match with one another. Major mismatches between both records occur synchronously in the Maldives and Bahamas periplatform sites and seem to correspond to extreme events of either carbonate-preservation or dissolution in the deep pelagic carbonate sites of the equatorial Pacific Ocean. Based on our findings, short- and long-term aragonite cycles can no longer be explained only by variations of aragonite input from the nearby shallow carbonate banks, in response to their alternate flooding and exposure through cyclic sea-level fluctuations. The aragonite long-term cycles in the periplatform environments are interpreted as carbonatepreservation cycles at intermediate-water depths. Their occurrence shows, therefore, that the carbonate chemistry of the entire water column has been influenced by long-term (0.5 m.y.) cyclic variations during the past 2.0 m.y. These major changes of the water-column carbonate chemistry are linked to the climate-induced carbon cycling among the different atmospheric, oceanic, and sedimentary carbon reservoirs.

Geochemistry of volcaniclastites of the western Pacific Ocean

Samples collected from the coarse basal portions of mid-Cretaceous volcaniclastic turbidites from the Mariana and Pigafetta basins are remarkably similar in terms of the petrographic and chemical features of their igneous clasts and bulk rock composition. Clasts of magmatic origin are dominated by glassy vesicular shards, variably phyric, holocrystalline basalts, and crystal fragments (olivine, clinopyroxene, plagioclase, amphibole, and biotite). The composition of the pyroxenes and amphiboles are typical of those found in differentiated hydrous alkali basalts. The bulk chemical composition of the volcaniclastites (based on stable incompatible elements and their ratios in highly vitric samples) is characteristic of alkali basalts found in within-plate oceanic eruptive environments. Miocene volcaniclastites from Site 802 are broadly similar to the Cretaceous samples in terms of clast type and bulk composition, and have also been derived from an oceanic alkali basalt source. The chemistry of the Miocene volcaniclastites differ, however, in having distinctive Zr/Y and Zr/Nb ratios and a more restricted chemical composition. The magmatic products of nearly emergent seamounts within the western Pacific basins appears to have been dominated by alkali basalt volcanism during the mid-Cretaceous and also the Miocene. The highly vitric nature of the Cretaceous and Miocene volcaniclastites, together with the morphology and vesicularity of their shards, suggests that they are the reworked (via mass flow) products of hyaloclastite accumulations produced in a shallow-water eruptive environment, such as that adjacent to nearly emergent seamounts or ocean islands. The association of ooids, reefal debris, and, in rare cases, woody material with the volcaniclastites supports their shallow-water derivation.

Mineralogy and major-element chemistry of volcanic ash of ODP Site 131-808

Mineralogical and major-element compositions of 72 samples of volcanic ash, recovered from Site 808 at Nankai Trough during Leg 131, were analyzed in relation to the early diagenetic alteration. Alteration products are first observed at the following depths: smectite, 200 mbsf; clinoptilolite, 646 mbsf; and analcite, 810 mbsf. Glass decomposition dominates over authigenic mineral formation between 200 and 550 mbsf in the sediment column, whereas mineral formation becomes dominant below 550 mbsf. Based on the X-ray diffraction patterns, a broad and asymmetric peak of 15A suggests a presence of illite/smectite (I/S) mixed-layered minerals in a sample from 646 mbsf. I/S mixed-layered mineral formation, however, rarely occurs even at the bottom of the sediment column (1290 mbsf) at 120° C. This is possibly because zeolite (especially clinoptilolite) formed in the ash interferes with illite formation in the smectite. The formation of alteration minerals affects the major-element chemistry of the ash and the interstitial waters. H4SiO4 concentrations in interstitial waters increase during glass decomposition and decrease with smectite and clinoptilolite formation. K is removed from interstitial water into smectite and/or clinoptilolite. Mg is fixed into smectite (and/or chlorite).