Mineral composition, rare earth elements, and trace elements from samples of the northern Congo deep-sea fan

Authigenic carbonates were collected from methane seeps at Hydrate Hole at 3113 m water depth and Diapir Field at 2417 m water depth on the northern Congo deep-sea fan during RV Meteor cruise M56. The carbonate samples analyzed here are nodules, mainly composed of aragonite and high-Mg calcite. Abundant putative microbial carbonate rods and associated pyrite framboids were recognized within the carbonate matrix. The d13C values of the Hydrate Hole carbonates range from -62.5 permil to -46.3 permil PDB, while the d13C values of the Diapir Field carbonate are somewhat higher, ranging from -40.7 permil to -30.7 permil PDB, indicating that methane is the predominant carbon source at both locations. Relative enrichment of 18O (d18O values as high as 5.2 permil PDB) are probably related to localized destabilization of gas hydrate. The total content of rare earth elements (REE) of 5% HNO3-treated solutions derived from carbonate samples varies from 1.6 ppm to 42.5 ppm. The shale-normalized REE patterns all display positive Ce anomalies (Ce/Ce* > 1.3), revealing that the carbonates precipitated under anoxic conditions. A sample from Hydrate Hole shows a concentric lamination, corresponding to fluctuations in d13C values as well as trace elements contents. These fluctuations are presumed to reflect changes of seepage flux.

The nature of LINER galaxies: Ubiquitous hot old stars and rare accreting black holes

Context. Galaxies, which often contain ionised gas, sometimes also exhibit a so-called low-ionisation nuclear emission line region (LINER). For 30 years, this was attributed to a central mass-accreting supermassive black hole (more commonly known as active galactic nucleus, AGN) of low luminosity, making LINER galaxies the largest AGN sub-population, which dominate in numbers over higher luminosity Seyfert galaxies and quasars. This, however, poses a serious problem. While the inferred energy balance is plausible, many LINERs clearly do not contain any other independent signatures of an AGN. Aims. Using integral field spectroscopic data from the CALIFA survey, we compare the observed radial surface brightness profiles with what is expected from illumination by an AGN. Methods. Essential for this analysis is a proper extraction of emission lines, especially weak lines, such as Balmer H beta lines, which are superposed on an absorption trough. To accomplish this, we use the GANDALF code, which simultaneously fits the underlying stellar continuum and emission lines. Results. For 48 galaxies with LINER-like emission, we show that the radial emission-line surface brightness profiles are inconsistent with ionisation by a central point-source and hence cannot be due to an AGN alone. Conclusions. The most probable explanation for the excess LINER-like emission is ionisation by evolved stars during the short but very hot and energetic phase known as post-AGB. This leads us to an entirely new interpretation. Post-AGB stars are ubiquitous and their ionising effect should be potentially observable in every galaxy with the gas present and with stars older than ~1 Gyr unless a stronger radiation field from young hot stars or an AGN outshines them. This means that galaxies with LINER-like emission are not a class defined by a property but rather by the absence of a property. It also explains why LINER emission is observed mostly in massive galaxies with old stars and little star formation.

The survey for ionization in neutral gas galaxies. I. Description and initial results

We introduce the Survey for Ionization in Neutral Gas Galaxies (SINGG), a census of star formation in H I selected galaxies. The survey consists of H alpha and R-band imaging of a sample of 468 galaxies selected from the H I Parkes All Sky Survey (HIPASS). The sample spans three decades in H I mass and is free of many of the biases that affect other star-forming galaxy samples. We present the criteria for sample selection, list the entire sample, discuss our observational techniques, and describe the data reduction and calibration methods. This paper focuses on 93 SINGG targets whose observations have been fully reduced and analyzed to date. The majority of these show a single emission line galaxy (ELG). We see multiple ELGs in 13 fields, with up to four ELGs in a single field. All of the targets in this sample are detected in H alpha, indicating that dormant (non-star-forming) galaxies with M-H I greater than or similar to 3x10(7) M-circle dot are very rare. A database of the measured global properties of the ELGs is presented. The ELG sample spans 4 orders of magnitude in luminosity (H alpha and R band), and H alpha surface brightness, nearly 3 orders of magnitude in R surface brightness and nearly 2 orders of magnitude in H alpha equivalent width (EW). The surface brightness distribution of our sample is broader than that of the Sloan Digital Sky Survey (SDSS) spectroscopic sample, the EW distribution is broader than prism-selected samples, and the morphologies found include all common types of star-forming galaxies (e.g., irregular, spiral, blue compact dwarf, starbursts, merging and colliding systems, and even residual star formation in S0 and Sa spirals). Thus, SINGG presents a superior census of star formation in the local universe suitable for further studies ranging from the analysis of H II regions to determination of the local cosmic star formation rate density.

He isotope, U/Th isotope, Calcium carbonate, biogenic opal, rare earth element concentrations, and grain size distribution measured on core-top sediments during SONNE cruise SO202 (INOPEX)

Eolian dust is a significant source of iron and other nutrients that are essential for the health of marine ecosystems and potentially a controlling factor of the high nutrient-low chlorophyll status of the Subarctic North Pacific. We map the spatial distribution of dust input using three different geochemical tracers of eolian dust, 4He, 232Th and rare earth elements, in combination with grain size distribution data, from a set of core-top sediments covering the entire Subarctic North Pacific. Using the suite of geochemical proxies to fingerprint different lithogenic components, we deconvolve eolian dust input from other lithogenic inputs such as volcanic ash, ice-rafted debris, riverine and hemipelagic input. While the open ocean sites far away from the volcanic arcs are dominantly composed of pure eolian dust, lithogenic components other than eolian dust play a more crucial role along the arcs. In sites dominated by dust, eolian dust input appears to be characterized by a nearly uniform grain size mode at ~4 µm. Applying the 230Th-normalization technique, our proxies yield a consistent pattern of uniform dust fluxes of 1-2 g/m**2/yr across the Subarctic North Pacific. Elevated eolian dust fluxes of 2-4 g/m**2/yr characterize the westernmost region off Japan and the southern Kurile Islands south of 45° N and west of 165° E along the main pathway of the westerly winds. The core-top based dust flux reconstruction is consistent with recent estimates based on dissolved thorium isotope concentrations in seawater from the Subarctic North Pacific. The dust flux pattern compares well with state-of-the-art dust model predictions in the western and central Subarctic North Pacific, but we find that dust fluxes are higher than modeled fluxes by 0.5-1 g/m**2/yr in the northwest, northeast and eastern Subarctic North Pacific. Our results provide an important benchmark for biogeochemical models and a robust approach for downcore studies testing dust-induced iron fertilization of past changes in biological productivity in the Subarctic North Pacific.

Analisi del comportamento di serbatoi di gas naturale liquefatto per applicazioni di propulsione navale in scenari di incendio

Il presente lavoro di tesi vuole focalizzare l’attenzione sull’impiego del GNL per la propulsione navale, analizzando aspetti legati alla sicurezza delle infrastrutture necessarie a tale scopo. Si sono considerati due diversi casi di studio: il primo riguarda un deposito costiero attrezzato per poter svolgere attività di rifornimento per imbarcazioni, mentre il secondo caso interessa una nave da trasporto passeggeri alimentata a GNL. È stata condotta un’analisi del rischio: l’identificazione dei pericoli ha seguito le linee guida proposte dalla metodologia MIMAH, oltre a sfruttare risultati di analisi HAZOP e HAZID. La stima delle frequenze di rilascio è stata effettuata con la tecnica della parts count, sulla base di valori ottenuti da database affidabilistici. La valutazione delle conseguenze è stata realizzata con il supporto del software DNV PHAST, utilizzando come riferimento i valori soglia proposti dal D.M. 9/5/2001. È stata infine impostata una modellazione fluidodinamica con lo scopo di valutare la possibilità di rottura catastrofica dei serbatoi di stoccaggio dovuta ad un’eccessiva pressurizzazione causata da una situazione di incendio esterno. Le simulazioni sono state condotte con il supporto del software CFD ANSYS® FLUENT® 17.2. Si è modellata una situazione di completo avvolgimento dalle fiamme considerando due geometrie di serbatoio diverse, nel caso di materiale isolante integro o danneggiato. I risultati ottenuti dall’analisi del rischio mostrano come i danni derivanti da un ipotetico scenario incidentale possano avere conseguenze anche significative, ma con valori di frequenze di accadimento tipici di situazioni rare. Lo studio fluidodinamico del comportamento di serbatoi di stoccaggio avvolti dalle fiamme ha evidenziato come questi siano capaci di resistere a condizioni gravose di incendio per tempi prolungati senza che si abbia una pressurizzazione tale da destare preoccupazione per l’integrità strutturale delle apparecchiature.

Electrochemistry of Heteroleptic Tris(phthalocyaninato) Rare Earth(III) Complexes

The electrochemical characteristics of a series of heteroleptic tris(phthalocyaninato) complexes with identical rare earths or mixed rare earths (Pc)M(OOPc)M(OOPc) [M = Eu...Lu, Y; H2Pc = unsubstituted phthalocyanine, H2(OOPc) = 3,4,12,13,21,22,30,31-octakis(octyloxy)phthalocyanine] and (Pc)Eu(OOPc)Er(OOPc) have been recorded and studied comparatively by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in CH2Cl2 containing 0.1 M tetrabutylammonium perchlorate (TBAP). Up to five quasi-reversible one-electron oxidations and four one-electron reductions have been revealed. The half-wave potentials of the first, second and fifth oxidations depend on the size of the metal center, but the fifth changes in the opposite direction to that of the first two. Moreover, the difference in redox potentials of the first oxidation and first reduction for (Pc)M(OOPc)M(OOPc), 0.85−0.98 V, also decreases linearly along with decreasing rare earth ion radius, clearly showing the rare earth ion size effect and indicating enhanced π−π interactions in the triple-deckers connected by smaller lanthanides. This order follows the red-shift seen in the lowest energy band of triple-decker compounds. The electronic differences between the lanthanides and yttrium are more apparent for triple-decker sandwich complexes than for the analogous double-deckers. By comparing triple-decker, double-decker and mononuclear [ZnII] complexes containing the OOPc ligand, the HOMO−LUMO gap has been shown to contract approximately linearly with the number of stacked phthalocyanine ligands.

Sandwich complexes of naphthalocyanine with the rare earth metals

Over the past two decades and in particular the past five years, numerous sandwich-type rare earth complexes containing naphthalocyanine ligands have been synthesized. The more extended delocalized π-electron system of naphthalocyanine in comparison with phthalocyanine generates unique physical, spectroscopic, electrochemical and photoelectrochemical properties which have aroused significant research interest in these compounds. This review summarizes recent progress in research on this important class of molecular materials and overviews the current status of the field.

Synthesis and characterization of K2Ca5(SO4)6· H2O, the equivalent of görgeyite, a rare evaporite mineral

Görgeyite, K2Ca5(SO4)6··H2O, is a very rare monoclinic double salt found in evaporites related to the slightly more common mineral syngenite. At 1 atmosphere with increasing external temperature from 25 to 150 °C, the following succession of minerals was formed: first gypsum and K2O, followed at 100 °C by görgeyite. Changes in concentration at 150 °C due to evaporation resulted in the formation of syngenite and finally arcanite. Under hydrothermal conditions, the succession is syngenite at 50 °C, followed by görgyeite at 100 and 150 °C. Increasing the synthesis time at 100 °C and 1 atmosphere showed that initially gypsum was formed, later being replaced by görgeyite. Finally görgeyite was replaced by syngenite, indicating that görgeyite is a metastable phase under these conditions. Under hydrothermal conditions, syngenite plus a small amount of gypsum was formed, after two days being replaced by görgeyite. No further changes were observed with increasing time. Pure görgeyite showed elongated crystals approximately 500 to 1000 µ m in length. The infrared and Raman spectra are mainly showing the vibrational modes of the sulfate groups and the crystal water (structural water). Water is characterized by OH-stretching modes at 3526 and 3577 cm–1 , OH-bending modes at 1615 and 1647 cm–1 , and an OH-libration mode at 876 cm–1 . The sulfate 1 mode is weak in the infrared but showed strong bands at 1005 and 1013 cm–1 in the Raman spectrum. The 2 mode also showed strong bands in the Raman spectrum at 433, 440, 457, and 480 cm–1 . The 3 mode is characterized by a complex set of bands in both infrared and Raman spectra around 1150 cm–1 , whereas 4 is found at 650 cm–1.

Comparative Electrochemical Study of Unsubstituted and Substituted Bis(phthalocyaninato) Rare Earth(III) Complexes

The electrochemistry of homoleptic substituted phthalocyaninato rare earth double-decker complexes M(TBPc)2 and M(OOPc)2 [M = Y, La...Lu except Pm; H2TBPc = 3(4),12(13),21(22),30(31)-tetra-tert-butylphthalocyanine, H2OOPc = 3,4,12,13,21,22,30,31-octakis(octyloxy)phthalocyanine] has been comparatively studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in CH2Cl2 containing 0.1 M tetra-n-butylammonium perchlorate (TBAP). Two quasi-reversible one-electron oxidations and three or four quasi-reversible one-electron reductions have been revealed for these neutral double-deckers of two series of substituted complexes, respectively. For comparison, unsubstituted bis(phthalocyaninato) rare earth analogues M(Pc)2 (M = Y, La...Lu except Pm; H2Pc = phthalocyanine) have also been electrochemically investigated. Two quasi-reversible one-electron oxidations and up to five quasi-reversible one-electron reductions have been revealed for these neutral double-decker compounds. The three bis(phthalocyaninato)cerium compounds display one cerium-centered redox wave between the first ligand-based oxidation and reduction. The half-wave potentials of the first and second oxidations and first reduction for double-deckers of the tervalent rare earths depend on the size of the metal center. The difference between the redox potentials of the second and third reductions for MIII(Pc)2, which represents the potential difference between the first oxidation and first reduction of [MIII(Pc)2]−, lies in the range 1.08−1.37 V and also gradually diminishes along with the lanthanide contraction, indicating enhanced π−π interactions in the double-deckers connected by the smaller, lanthanides. This corresponds well with the red-shift of the lowest energy band observed in the electronic absorption spectra of reduced double-decker [MIII(Pc′)2]− (Pc′ = Pc, TBPc, OOPc).

Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes : (Part 10) The infrared and Raman characteristics of phthalocyanine in heteroleptic bis(phthalocyaninato) rare earth complexes with decreased molecular symmetry

The infrared (IR) spectroscopic data for a series of eleven heteroleptic bis(phthalocyaninato) rare earth complexes MIII(Pc)[Pc(α-OC5H11)4] (M = Sm–Lu, Y) [H2Pc = unsubstituted phthalocyanine, H2Pc(α-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine] have been collected with 2 cm−1 resolution. Raman spectroscopic properties in the range of 500–1800 cm−1 for these double-decker molecules have also been comparatively studied using laser excitation sources emitting at 632.8 and 785 nm. Both the IR and Raman spectra for M(Pc)[Pc(α-OC5H11)4] are more complicated than those of homoleptic bis(phthalocyaninato) rare earth analogues due to the decreased molecular symmetry of these double-decker compounds, namely C4. For this series, the IR Pc√− marker band appears as an intense absorption at 1309–1317 cm−1, attributed to the pyrrole stretching. With laser excitation at 632.8 nm, Raman vibrations derived from isoindole ring and aza stretchings in the range of 1300–1600 cm−1 are selectively intensified. In contrast, when excited with laser radiation of 785 nm, the ring radial vibrations of isoindole moieties and dihedral plane deformations between 500 and 1000 cm−1 for M(Pc)[Pc(α-OC5H11)4] intensify to become the strongest scatterings. Both techniques reveal that the frequencies of pyrrole stretching, isoindole breathing, isoindole stretchings, aza stretchings and coupling of pyrrole and aza stretchings depend on the rare earth ionic size, shifting to higher energy along with the lanthanide contraction due to the increased ring-ring interaction across the series. The assignments of the vibrational bands for these compounds have been made and discussed in relation to other unsubstituted and substituted bis(phthalocyaninato) rare earth analogues, such as M(Pc)2 and M(OOPc)2 [H2OOPc = 2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyanine].