Radon 222 excess measured on water bottle samples during HEINCKE cruise HE153

In the years 2000 and 2001 we measured methane concentrations exceeding up to two orders of magnitude the equilibrium with the atmosphere in the water column on the SW-Spitsbergen continental shelf. This methane anomaly extended from its centre on the shelf westwards over the upper slope and eastwards well into the inner basins of the two southernmost Spitsbergen fjords, the Hornsundfjord and the van Mijenfjord. Methane concentrations and stable carbon isotopic ratios varied between 2 and 240 nM, and between -53 per mill and -20 per mill VPDB, respectively. Methane in high concentrations was depleted in 13C whereas in low concentrations d13CCH4 values were highly variable. On the continental shelf we found that methane discharged from seeps on top of sandy and gravelly banks is isotopically heavier than methane escaping from troughs filled with silty and clayey sediments. These distinct isotopic signatures suggest that methane is gently released from several inter-granular seepages or micro-seepages widely spread over the shelf. A potential migration path for thermogenic or hydrate methane may be the Hornsund Fracture Zone, a south-north running reactivated fault system created by stretching of the continental crust. After discharge into the water column, local water currents fed by Atlantic water, coastal water, and freshwater outflows from the fjords further determine pathways and fate of the methane. We used d18Owater and 222Rn data to trace origin and advection of the local water masses and water mixing processes. Methane spreads predominantly along pycnoclines and by vertical mixing. During transport methane is influenced simultaneously by oxidation and dilution, as well as loss into the atmosphere. Together these processes cause the spatial variability of the anomaly and heterogeneity in d13CCH4 in this polar shelf environment.

(Table 1) Composition of pore water from ODP Site 997 holes A and B

Pore water extracted from sediments penetrated on Leg 164 of the Ocean Drilling Program at the Blake Ridge West. Atlantic were analyzed for acetate, total dissolved organic carbon, bromide and iodide, to help explain the occurrence of subsurface maxima in bacteria biomass and activity reported previously from a nearby site. The high concentrations of these organic matter decomposition by-products in the pore waters from sediments with moderate concentrations of sedimentary organic matter can convincingly be modelled as resulting from upward migration of pore water. The amount of acetate and unidentified DOC transported by the pore water contribute significantly to the pool of metabolizable carbon, and may be the most important substances in energetic terms.

(Table 1) Carbon, hydrocarbons and observations at DSDP Holes 67-497 and 67-498A

Gas hydrates are icelike materials that form when specific conditions of temperature, pressure, and gas composition are simultaneously satisfied. Among the first descriptions of gas hydrates under natural conditions was that of Hammerschmidt (1940), who found them in pipelines used to transport natural gas. Milton (1976) indicates that conditions are suitable for the presence of gas hydrates in areas affected by permafrost and cites studies suggesting that large quantities of gas exist in hydrate form.

Soft solution processing of cerium hydroxysulfate powders with different morphologies

Polycrystalline cerium hydroxysulfate powders have been prepared by soft solution processing using various basic solvents. The crystals prepared have varying morphologies, spherical and flaky, depending on the solvent used. The crystals obtained from distilled water-pyridine and aqueous ammonia solvent mixtures are spherical, whereas those obtained from mixtures of distilled water and ethylenediamine or hydrazine hydrate are flaky. All the crystalline cerium hydroxysulfate samples display luminescence properties. It was found that the flaky crystals generally show a much stronger luminescence than their spherical counterparts.

Molecular dynamics characterization of n-octyl-beta-D-glucopyranoside micelle structure in aqueous solution

n-Octyl-beta-D-glueopyranoside (OG) is a non-ionic glycolipid, which is used widely in biotechnical and biochemical applications. All-atom molecular dynamics simulations from two different initial coordinates and velocities in explicit solvent have been performed to characterize the structural behaviour of an OG aggregate at equilibrium conditions. Geometric packing properties determined from the simulations and small angle neutron scattering experiment state that OG micelles are more likely to exist in a non-spherical shape, even at the concentration range near to the critical micelle concentration (0.025 M). Despite few large deviations in the principal moment of inertia ratios, the average micelle shape calculated from both simulations is a prolate ellipsoid. The deviations at these time scales are presumably the temporary shape change of a micelle. However, the size of the micelle and the accessible surface areas were constant during the simulations with the micelle surface being rough and partially elongated. Radial distribution functions computed for the hydroxyl oxygen atoms of an OG show sharper peaks at a minimum van der Waals contact distance than the acetal oxygen, ring oxygen, and anomeric carbon atoms. This result indicates that these atoms are pointed outwards at the hydrophilic/hydrophobic interface, form hydrogen bonds with the water molecules, and thus hydrate the micelle surface effectively. (c) 2005 Elsevier Inc. All rights reserved.

Synthesis and structure characterization of chromium oxide prepared by solid thermal decomposition reaction

Mesoporous chromium oxide (Cr2O3) nanocrystals were first synthesized by the thermal decomposition reaction of Cr(NO3)(3)(circle)9H(2)O using citric acid monohydrate (CA) as the mesoporous template agent. The texture and chemistry of chromium oxide nanocrystals were characterized by N-2 adsorption-desorption isotherms, FTIR, X-ray diffraction (XRD), UV-vis, and thermoanalytical methods. It was shown that the hydrate water and CA are the crucial factors in influencing the formation of mesoporous Cr2O3 nanocrystals in the mixture system. The decomposition of CA results in the formation of a mesoporous structure with wormlike pores. The hydrate water of the mixture provides surface hydroxyls that act as binders, making the nanocrystals aggregate. The pore structures and phases of chromium oxide are affected by the ratio of precursor-to-CA, thermal temperature, and time.

Geochemical and Sr, Nd, Pb isotope investigation of the New Caledonia ophiolite

The New Caledonia ophiolite hosts one of the largest obducted mantle section in the world, hence providing a unique insight for the study of upper mantle processes. These mantle rocks belong to an “atypical” ophiolitic sequence, which is dominated by refractory harzburgites but it also includes minor spinel and plagioclase lherzolites. Upper crust is notably absent in the ophiolite, with the exception of some mafic-ultramafic cumulates cropping out in the southern part of the island. Although the New Caledonia ophiolite has been under investigation for decades, its ultra-depleted nature has made its characterization an analytical challenge, so that few trace element data are available, while isotopic data are completely missing. In this thesis a comprehensive geochemical study (major, trace element and Sr-Nd-Pb isotopes) of the peridotites and the associated intrusive mafic rocks from the New Caledonia ophiolite has been carried out. The peridotites are low-strain tectonites showing porphyroclastic textures. Spinel lherzolites are undepleted lithotypes, as attested by the presence of 7-8 vol% of Na2O and Al2O3-rich clinopyroxene (up to 0.5 wt% Na2O; 6.5 wt% Al2O3), Fo content of olivine (88.5-90.0 mol%) and low Cr# of spinel (13-17). Conversely, harzburgites display a refractory nature, proven by the remarkable absence of primary clinopyroxene, very high Fo content in olivine (90.9-92.9 mol%), high Mg# in orthopyroxene (89.8-94.2) and Cr# in spinel (39-71). REE contents show abyssal-type patterns for spinel lherzolites, while harzburgites display U-shaped patterns, typical of fore-arc settings. Spinel lherzolites REE compositions are consistent with relatively low degree (8-9%) of fractional melting of a DMM source, starting in the garnet stability field. Conversely, REE models for harzburgites indicate high melting degrees (20-25%) of a DMM mantle source under spinel faies conditions, consistent with hydrous melting in forearc setting. Plagioclase lherzolites exhibit melt impregnation microtextures, Cr- and TiO2-enriched spinels and REE, Ti, Y, Zr progressive increase with respect to spinel lherzolites. Impregnation models indicate that plagioclase lherzolites may derive from spinel lherzolites by entrapment of highly depleted MORB melts in the shallow oceanic lithosphere. Mafic intrusives are olivine gabbronorites with a very refractory composition, as attested by high Fo content of olivine (87.3-88.9 mol.%), very high Mg# of clinopyroxene (87.7-92.2) and extreme anorthitic content of plagioclase (An = 90-96 mol%). The high Mg#, low TiO2 concentrations in pyroxenes and the anorthitic composition of plagioclase point out an origin from ultra-depleted primitive magmas in a convergent setting. Geochemical trace element models show that the parental melts of gabbronorites are primitive magmas with striking depleted compositions, bearing only in part similarities with the primitive boninitic melts of Bonin Islands. The first Sr, Nd and Pb isotope data obtained for the New Caledonia ophiolite highlight the presence of DM mantle source variably modified by different processes. Nd-Sr-Pb isotopic ratios for the lherzolites (+6.98≤epsilon Ndi≤+10.97) indicate a DM source that suffered low-temperature hydrothermal reactions. Harzburgites are characterized by a wide variation of Sr, Nd and Pb isotopic values, extending from DM-type to EM2 compositions (-0.82≤ epsilon Ndi≤+17.55), suggesting that harzburgite source was strongly affected by subduction-related processes. Conversely, combined trace element and Sr-Nd-Pb isotopic data for gabbronorites indicate a derivation from a source with composition similar to Indian-type mantle, but affected by fluid input in subduction environment. These geochemical features point out an evolution in a pre-Eocenic marginal basin setting, possibly in the proximity of a transform fault, for the lherzolites. Conversely, the harzburgites acquired their main geochemical and isotopic fingerprint in subduction zone setting.

Synthesis and characterization of triazolotriazines

The Dimroth rearrangement in ring-fused 1,2,4-triazoles has been reviewed in detail in Part I and the synthesis of all known triazolo-triazines is described in Part II. Experimental investigations concerned the establishinent of the skeletal arrangement of a variety of triazolotriazines formed by several synthetic routes. Interaction of 3-amino-5-hydrazino-12,4-triazole and benzilafforded 2-amino-6, 7-diphenyl-1, 2,4-triazolo[ 5, 1-c-]-1,2,4-triazine,whereas cyclization of 5,6-diphenyl-3-hydrazino-1,2,4-triazine withcyanogen bromide resulted in the isomeric 3-amino-6,7-diphenyl,-1,2,4-triazolo [4, 3-b]-1,2,4-triazine: both amines were deaminated with amyl nitrite in boiling tetrahydrofuran without rearrangement of the heterocyclic skeleton. 6,7-Diphenyl-1,2,4-triazolo[5,1-cJ-1,2.4-triazine, synthesized from 3-hydrazino-1,2,4-triazole and benzil, formed a covalent hydrate which could be detected spectroscopically in solution, and a covalemt methanolate and ethanolate which could be isolated. A new route to 3-amino-5-hydrazino-pyrazole is described and cyclization to 7-amino-3,4-diphenyl-pyrazolo[ 5,1-.c]-1,2,4-triazine was achieved with benzil. The diazonium nitrate of 3-amino-1,2,4-triazole coupled with ethyl cyanoacetate to yield a mixture of two geometrical isomers of ethyl 2-(2H-1,2,4-triazol-3-ylhydrazono) cyanoacetate.Recrystallization of the crude coupling mixture from aqueous ethanol gave a single hydra-zone which cyclized predominantly to ethyl 7-amino-1,2,4-triazolo[5,1-c]-1,2,4-triazine-6-carboxylate in acid conditions and 6-cyano-1,2,4-triazolo[ 5,1-c]-1,2,4~triazin-7(4H)-one under basic conditions. The nature of the cyclizing medium also controlled the cyclization of .the (pyrazol-ylhydrazono) cyanoacetate hut the corresponding (tetrazol- ylhydrazono) cyanoacetate gave only ethyl 7-aminotetrazolo[ 5,1-cJ-1,2,4- -triazine-6-carboxylate. 2-( 2H-1,2,4-Triazol-3-:ylhydrazono) malonitrile cyclized unambiguously to 7-amino-6-cyano-1,2,4-triazolo-[ 5,1-c]-1,2,4- triazine. Drastic hydrolysis of ethyl 2-(2H-1,2,4-triazol-3-yllhydrazono)-cyanoacetate, ethyl 7-amino-1, 2,4-triazolo[ 5,1-c]-1,2,4-triazine-6-carboxylate, 6-cyano-1,2,4-triazolo[ 5,1-c]-1,2,4-triazin-7{ 4H)-one and 7-amino-6- cyano-1,2,4-triazolo[5,1-c]-1,2,4-triazine gave a hydrate of 1,2,4-triazo1o[5,1-c ]-1,2,4-triazin-7(4H)-one. Mass spectral fragmentations of 7-aminoazolo-[5,1-c]-1,2,4-triazinesconfirm that the azole ring is more stable than the 1,2,4-triazine ring on electron impact.

Monte Carlo and molecular dynamics simulations of methane in potassium montmorillonite clay hydrates at elevated pressures and temperatures

The structure and dynamics of methane in hydrated potassium montmorillonite clay have been studied under conditions encountered in sedimentary basin and compared to those of hydrated sodium montmorillonite clay using computer simulation techniques. The simulated systems contain two molecular layers of water and followed gradients of 150 barkm-1 and 30 Kkm-1 up to a maximum burial depth of 6 km. Methane particle is coordinated to about 19 oxygen atoms, with 6 of these coming from the clay surface oxygen. Potassium ions tend to move away from the center towards the clay surface, in contrast to the behavior observed with the hydrated sodium form. The clay surface affinity for methane was found to be higher in the hydrated K-form. Methane diffusion in the two-layer hydrated K-montmorillonite increases from 0.39×10-9 m2s-1 at 280 K to 3.27×10-9 m2s-1 at 460 K compared to 0.36×10-9 m2s-1 at 280 K to 4.26×10-9 m2s-1 at 460 K in Na-montmorillonite hydrate. The distributions of the potassium ions were found to vary in the hydrates when compared to those of sodium form. Water molecules were also found to be very mobile in the potassium clay hydrates compared to sodium clay hydrates. © 2004 Elsevier Inc. All All rights reserved.

CuII chain compound showing a ferromagnetic coupling through triple N1,N2-1,2,4-triazole bridges

[Cu(hyetrz)3](CF3SO3)2·H2O [hyetrz = 4-(2′-hydroxyethyl)-1,2,4-triazole] represents the first structurally characterised ferromagnetically coupled CuII chain compound containing triple N1,N2-1,2,4-triazole bridges. catena-[μ-Tris{4-(2′-hydroxyethyl)-1,2,4-triazole-N1,N2}copper(II)] bis(trifluoromethanesulfonate) hydrate (C14H23F6S2O10CuN9) crystallises in the triclinic space group Pl, a = 13.54(3), b = 14.37(3), c = 15.61(4) Å, α = 95.9(1), β = 104.9(1), γ = 106.5(1)°, V = 2763(11) Å3, Z = 4 (CuII units). The CuII ions are linked by triple N1,N2-1,2,4-triazole bridges yielding an alternating chain with Cu1−Cu2 = 3.8842(4) Å and Cu2−Cu3 = 3.9354(4) Å. Analysis of the magnetic data according to a high-temperature series expansion gives a J value of +1.45(3) cm−1. The nature and the magnitude of the ferromagnetic exchange have been discussed on the basis of the structural features. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).

Novel analytical methodologies for the monitoring of traditional and non-traditional pollutants in different environmental compartments of South Florida

Routine monitoring of environmental pollution demands simplicity and speed without sacrificing sensitivity or accuracy. The development and application of sensitive, fast and easy to implement analytical methodologies for detecting emerging and traditional water and airborne contaminants in South Florida is presented. A novel method was developed for quantification of the herbicide glyphosate based on lyophilization followed by derivatization and simultaneous detection by fluorescence and mass spectrometry. Samples were analyzed from water canals that will hydrate estuarine wetlands of Biscayne National Park, detecting inputs of glyphosate from both aquatic usage and agricultural runoff from farms. A second study describes a set of fast, automated LC-MS/MS protocols for the analysis of dioctyl sulfosuccinate (DOSS) and 2-butoxyethanol, two components of Corexit®. Around 1.8 million gallons of those dispersant formulations were used in the response efforts for the Gulf of Mexico oil spill in 2010. The methods presented here allow the trace-level detection of these compounds in seawater, crude oil and commercial dispersants formulations. In addition, two methodologies were developed for the analysis of well-known pollutants, namely Polycyclic Aromatic Hydrocarbons (PAHs) and airborne particulate matter (APM). PAHs are ubiquitous environmental contaminants and some are potent carcinogens. Traditional GC-MS analysis is labor-intensive and consumes large amounts of toxic solvents. My study provides an alternative automated SPE-LC-APPI-MS/MS analysis with minimal sample preparation and a lower solvent consumption. The system can inject, extract, clean, separate and detect 28 PAHs and 15 families of alkylated PAHs in 28 minutes. The methodology was tested with environmental samples from Miami. Airborne Particulate Matter is a mixture of particles of chemical and biological origin. Assessment of its elemental composition is critical for the protection of sensitive ecosystems and public health. The APM collected from Port Everglades between 2005 and 2010 was analyzed by ICP-MS after acid digestion of filters. The most abundant elements were Fe and Al, followed by Cu, V and Zn. Enrichment factors show that hazardous elements (Cd, Pb, As, Co, Ni and Cr) are introduced by anthropogenic activities. Data suggest that the major sources of APM were an electricity plant, road dust, industrial emissions and marine vessels.

Utilização da cinza da casca de arroz em cimentação de poços de petróleo

Pozzolanic materials such as rice husk ash are widely used to substitute part of cement, because they react with calcium hydroxide (CH) producing calcium silicate hydrate (C-S-H), which aggregate better physical, chemical and mechanical properties to the cement slurry. The usage of rice husk biomass ash from agribusiness in addition to or partially replacing cement is a noble purpose and a good way of sustainable development which currently is an obsession around the world. The ashes utilized in this study were characterized by: scanning electron microscopy technique (SEM), Fourier transform infrared spectroscopy (FTIR), Energy-dispersive X-ray spectroscopy (EDX) and BET method. The pozzolanic activity of RHA and WRHA in cement slurries was evaluated by: thermal-gravimetric technique and derivative thermogravimetry (TGA/DTG), X-ray diffraction (XRD) and Compressive Strength. The slurries formulated with additions of 10% and 20% of RHA and WRHA were cured for 28 days at 58 °C. The results of thermal analysis demonstrated that a 20% WRHA addition caused a reduction of approximately 73% of Portlandite (calcium hydroxide – CH) phase related to standard slurry (STD). The XRD scans also demonstrated the reduction of the Portlandite peaks’ intensity for each slurry compared with STD slurry. The RHA and WRHA react chemically with Portlandite producing calcium silicate hydrate (C-S-H), confirming their effect as a pozzolanic agent. The WRHA presented the best results as a pozzolanic material.

Investigations of artificial sediments from two deep-sea in situ recolonization experiments deployed for one year at the central HAUSGARTEN station IV during ARK-XIX/3c

Commercial exploitation and abrupt changes of the natural conditions may have severe impacts on the Arctic deep-sea ecosystem. The present recolonisation experiment mimicked a situation after a catastrophic disturbance (e.g. by turbidites caused by destabilized continental slopes after methane hydrate decomposition) and investigated if the recolonisation of a deep-sea habitat by meiobenthic organisms is fostered by variations innutrition and/or sediment structure. Two "Sediment Tray Free Vehicles" were deployed for one year in summer 2003 at 2500 m water depth in the Arctic deep-sea in the eastern Fram Strait. The recolonisation trays were filled with different artificial and natural sediment types (glass beads, sand, sediment mixture, pure deep-sea sediment) and were enriched with various types of food (algae, yeast, fish). After one year, meiobenthos abundances and various sediment related environmental parameters were investigated. Foraminifera were generally the most successful group: they dominated all treatments and accounted for about 87% of the total meiobenthos. Colonizing meiobenthos specimens were generally smaller compared to those in the surrounding deep-sea sediment, suggesting an active recolonisation by juveniles. Although experimental treatments with fine-grained, algae-enriched sediment showed abundances closest to natural conditions, the results suggest that food availability was the main determining factor for a successful recolonisation by meiobenthos and the structure of recolonised sediments was shown to have a subordinate influence.

CO2 concentration and stable isotope ratios of three Antarctic ice cores covering the period from 149.4 - 1.5 kyr before 1950

We present new d13C measurements of atmospheric CO2 covering the last glacial/interglacial cycle, complementing previous records covering Terminations I and II. Most prominent in the new record is a significant depletion in d13C(atm) of 0.5 permil occurring during marine isotope stage (MIS) 4, followed by an enrichment of the same magnitude at the beginning of MIS 3. Such a significant excursion in the record is otherwise only observed at glacial terminations, suggesting that similar processes were at play, such as changing sea surface temperatures, changes in marine biological export in the Southern Ocean (SO) due to variations in aeolian iron fluxes, changes in the Atlantic meridional overturning circulation, upwelling of deep water in the SO, and long-term trends in terrestrial carbon storage. Based on previous modeling studies, we propose constraints on some of these processes during specific time intervals. The decrease in d13C(atm) at the end of MIS 4 starting approximately 64 kyr B.P. was accompanied by increasing [CO2]. This period is also marked by a decrease in aeolian iron flux to the SO, followed by an increase in SO upwelling during Heinrich event 6, indicating that it is likely that a large amount of d13C-depleted carbon was transferred to the deep oceans previously, i.e., at the onset of MIS 4. Apart from the upwelling event at the end of MIS 4 (and potentially smaller events during Heinrich events in MIS 3), upwelling of deep water in the SO remained reduced until the last glacial termination, whereupon a second pulse of isotopically light carbon was released into the atmosphere.

Data on the biogeochemical cycle of methane in the ocean

Geological, mineralogical and microbiological aspects of the methane cycle in water and sediments of different areas in the oceans are under consideration in the monograph. Original and published estimations of formation- and oxidation rates of methane with use of radioisotope and isotopic methods are given. The role of aerobic and anaerobic microbial oxidation of methane in production of organic matter and in formation of authigenic carbonates is considered. Particular attention is paid to processes of methane transformation in areas of its intensive input to the water column from deep-sea hydrothermal sources, mud volcanoes, and cold methane seeps.