Coordination networks of Cu2+ ions with 1,3-bis[2-(4-pyridyl)ethyl]benzene : strong structure-directing role of the counter ion (nitrate, acetate and sulphate), leading to clusters, sheets and chains

Date of Acceptance: 16/10/2015

Crystal structures of two one-dimensional coordination polymers constructed from Mn2+ ions, chelating anions and flexible bipyridyl bridging ligands

Peer reviewed

Crystal structures of a family of layered coordination polymers containing divalent metal ions (Mn2+, Co2+, Ni2+ and Zn2+) and the 3-amino 4-methyl benzoate ion

Peer reviewed

Coordination networks of Cu2+ ions with 1,3-bis[2-(4-pyridyl)ethyl]benzene : strong structure-directing role of the counter ion (nitrate, acetate and sulphate), leading to clusters, sheets and chains

Date of Acceptance: 16/10/2015

Anomalous supply of bioessential molybdenum in mid-Proterozoic surface environments

Date of Acceptance: 29/12/2015 We are grateful to A. Sandison and W. Thayalon for skilled technical support, and Mike Porter and an anonymous reviewer, who helped to clarify the manuscript.

Systèmes RBS par ions lourds avec détecteur temps-de-vol

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Single-crystal micro/nanostructures and thin films of lamellar molybdenum oxide by solid-state pyrolysis of organometallic derivatives of a cyclotriphosphazene

The solid-state pyrolysis of organometallic derivatives of a cyclotriphosphazene is demonstrated to be a new, simple and versatile solid-state templating method for obtaining single-crystal micro- and nanocrystals of transition and valve metal oxides. The technique, when applied to Mo-containing organometallics N3P3[OC6H4CH2CN·Mo(CO)5]6 and N3P3[OC6H4CH2CN·Mo(CO)4 py]6, results in stand-alone and surface-deposited lamellar MoO3 single crystals, as determined by electron and atomic force microscopies and X-ray diffraction. The size and morphology of the resulting crystals can be tuned by the composition of the precursor. X-ray photoelectron and infrared spectroscopies indicate that the deposition of highly lamellar MoO3 directly on an oxidized (400 nm SiO2) surface or (100) single-crystal silicon surfaces yields a layered uniphasic single-crystal film formed by cluster diffusion on the surface during pyrolysis of the metal-carbonyl derivatives. For MoO3 in its layered form, this provides a new route to an important intercalation material for high energy density battery materials.

Systèmes RBS par ions lourds avec détecteur temps-de-vol

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Seawater carbonate chemistry and hydrogen ions and carbonate chemistry in calcifying fluid of coral Astrangia poculata during experiments, 2011

A generalized physicochemical model of the response of marine organisms' calcifying fluids to CO2-induced ocean acidification is proposed. The model is based upon the hypothesis that some marine calcifiers induce calcification by elevating pH, and thus Omega aragonite, of their calcifying fluid by removing protons (H+). The model is explored through two end-member scenarios: one in which a fixed number of H+ is removed from their calcifying fluid, regardless of atmospheric pCO2, and another in which a fixed external-internal proton ratio ([H+]E/[H+]I) is maintained. The model is able to generate the full range of calcification response patterns observed in prior ocean acidification experiments and is consistent with the assertion that organisms' calcification response to ocean acidification is more negative for marine calcifiers that exert weaker control over their calcifying fluid pH. The model is empirically evaluated for the temperate scleractinian coral Astrangia poculata with in situ pH microelectrode measurements of the coral's calcifying fluid under control and acidified conditions. These measurements reveal that (1) the pH of the coral's calcifying fluid is substantially elevated relative to its external seawater under both control and acidified conditions, (2) the coral's [H+]E/[H+]I remains constant under control and acidified conditions, and (3) the coral removes fewer H+ from its calcifying fluid under acidified conditions than under control conditions. Thus, the carbonate system dynamics of A. poculata's calcifying fluid appear to be most consistent with the fixed [H+]E/[H+]I end-member scenario. Similar microelectrode experiments performed on additional taxa are required to assess the model's general applicability.

Geochemistry of ODP Hole 176-735B igneous and hydrothermal veins

During Legs 118 and 176, Ocean Drilling Program Hole 735B, located on Atlantis Bank on the Southwest Indian Ridge, was drilled to a total depth of 1508 meters below seafloor (mbsf) with nearly 87% recovery. The recovered core provides a unique section of oceanic Layer 3 produced at an ultraslow spreading ridge. Metamorphism and alteration are extensive in the section but decrease markedly downward. Both magmatic and hydrothermal veins are present in the core, and these were active conduits for melt and fluid in the crust. We have identified seven major types of veins in the core: felsic and plagioclase rich, plagioclase + amphibole, amphibole, diopside and diopside + plagioclase, smectite ± prehnite ± carbonate, zeolite ± prehnite ± carbonate, and carbonate. A few epidote and chlorite veins are also present but are volumetrically insignificant. Amphibole veins are most abundant in the upper 50 m of the core and disappear entirely below 520 mbsf. Felsic and plagioclase ± amphibole ± diopside veins dominate between ~50 and 800 mbsf, and low-temperature smectite, zeolite, and prehnite veins are present in the lower 500 m of the core. Carbonate veinlets are randomly present throughout the core but are most abundant in the lower portions. The amphibole veins are closely associated with zones of intense crystal plastic deformation formed at the brittle/ductile boundary at temperatures above 700°C. The felsic and plagioclase-rich veins were formed originally by late magmatic fluids at temperatures above 800°C, but nearly all of these have been overprinted by intense hydrothermal alteration at temperatures between 300° and 600°C. The zeolite, prehnite, and smectite veins formed at temperatures <100°C. The chemistry of the felsic veins closely reflects their dominant minerals, chiefly plagioclase and amphibole. The plagioclase is highly zoned with cores of calcic andesine and rims of sodic oligoclase or albite. In the felsic veins the amphibole ranges from magnesio-hornblende to actinolite or ferro-actinolite, whereas in the monomineralic amphibole veins it is largely edenite and magnesio-hornblende. Diopside has a very narrow range of composition but does exhibit some zoning in Fe and Mg. The felsic and plagioclase-rich veins were originally intruded during brittle fracture at the ridge crest. The monomineralic amphibole veins also formed near the ridge axis during detachment faulting at a time of low magmatic activity. The overprinting of the igneous veins and the formation of the hydrothermal veins occurred as the crustal section migrated across the floor of the rift valley over a period of ~500,000 yr. The late-stage, low-temperature veins were deposited as the section migrated out of the rift valley and into the transverse ridge along the margin of the fracture zone.

Molybdenum and sulphur isotope ratios of early Pleistocene sapropels of ODP Hole 160-969D

Organic-rich sediments (sapropels) deposited in the Mediterranean are presumed to have formed during periods of increased productivity, and/or deep water oxygen depletion, possibly including the development of sulfidic conditions (euxinia). Geochemical redox proxies (Re, Mo, Mo isotopes, V, Fe/Al, and multiple S isotopes) in 8 sapropels from the Pleistocene confirm water column euxinic conditions of varying intensity during sapropel deposition. These same proxies indicate an oxic origin for hemipelagic sediments deposited between sapropel-forming episodes. In one intensively sampled sapropel, deposited between 1.450 and 1.458 Ma, changing concentrations of organic carbon, Ba, Re, Mo, V, and Fe/Al track one another closely, reflecting coupling between water column euxinia and biological productivity. Multiple S isotope data from this sapropel suggest that the redox interface where oxidative sulfur cycling occurred was present in the sediments during hemipelagic sedimentation, but moved into the water column during sapropel deposition. Molybdenum isotopes of these 8 sapropels encompass a range of values (d98Mo = +0.2 to +1.7), but are all 98Mo-depleted relative to seawater (d98Mo = +2.3 per mil), suggesting that quantitative removal of Mo did not occur. This finding contrasts with modern Black Sea sediments. In general, Re/Mo ratios in sapropels are greater than in modern seawater, implying that the water column was not sufficiently sulfidic during sapropel-forming episodes to induce complete removal of both these elements. Surprisingly, the heaviest d98Mo values are found within hemipelagic sediments. Very few of the hemipelagic samples preserve the negative d98Mo values commonly associated with modern oxic marine sediments. Many of the hemipelagic samples also contained higher concentrations of Re and Mo than are common in oxic sediments. These features may be attributable to diffusion from the sapropels of a 98Mo-enriched component into the hemipelagic sediments.

(Table II, page 668-669) Distribution of elements between minerals soluble in 1M Hydroxylamine hydrochloride (Reducible); in 1m HCL (Acid-soluble) and in the insoluble residue of manganese nodules

Attempts to classify pelagic sediments have been based either on appearance and composition, or on the ultimate origin of the components. In particular it appears feasible to distinguish minerals which crystallized in sea-water from those which formed in magmas, in hydrothermal solution, or by weathering under acidic conditions. It is the case of iron and manganese oxide mineral aggregates which constitute one of the major types of rock encountered on the ocean floor; according to Menard (unpublished) about 10% of the pelagic area of the Pacific is covered by such nodules. The nodules consist of intimately intergrown crystallites of different minerals among those identified, besides detrital minerals and organic matter, are opal, goethite, rutile, anatase, barite, nontronite, and at least three manganese oxide minerals of major importance. Arrhenius and Korkisch (1959) have attempted to separate from each other the different minerals constituting the nodules, in order to establish the details of their structure and the localization of the heavy metal ions. The results demonstrate (Table II) that copper and nickel are concentrated in the manganese oxide phases concentrated in the reducible fraction. Cobalt, part of the nickel and most of the chromium are distributed between these and the acid-soluble group of the non-manganese minerals, dominated by goethite and disordered FeOOH.

Numerical study of neutron beam divergence in a beam-fusion scenario employing laser driven ions

The most established route to create a laser-based neutron source is by employing laser accelerated, low atomic-number ions in fusion reactions. In addition to the high reaction cross-sections at moderate energies of the projectile ions, the anisotropy in neutron emission is another important feature of beam-fusion reactions. Using a simple numerical model based on neutron generation in a pitcher–catcher scenario, anisotropy in neutron emission was studied for the deuterium–deuterium fusion reaction. Simulation results are consistent with the narrow-divergence ( ∼ 70 ° full width at half maximum) neutron beam recently served in an experiment employing multi-MeV deuteron beams of narrow divergence (up to 30° FWHM, depending on the ion energy) accelerated by a sub-petawatt laser pulse from thin deuterated plastic foils via the Target Normal Sheath Acceleration mechanism. By varying the input ion beam parameters, simulations show that a further improvement in the neutron beam directionality (i.e. reduction in the beam divergence) can be obtained by increasing the projectile ion beam temperature and cut-off energy, as expected from interactions employing higher power lasers at upcoming facilities.