New data on the ophiolitic VMS deposits of Moeche (Cabo Ortegal Complex, NW Spain)

As a result of the variscan collision, several allochtonous complexes were emplaced on the Iberian margin in Devonian times, among them the Cabo Ortegal Complex comprising the Moeche ophiolitic sequence. Copper has been won from several mines (Piquitos I & II, Barqueira, Maruxa) from disseminated ores and thin massive sulphide layers in the Moeche Unit, a strongly deformed meta-volcanic sequence comprising mainly quartz-chlorite schists and mylonites, which defines the top of the ophiolite. The ores were metamorphosed and strongly deformed under brittle conditions (for pyrite), but their textures are often apparently post-deformational, due to very common solution-transfer processes; they are composed mostly of pyrite and chalcopyrite, with minor sphalerite, pyrrhotite, etc., and with traces of native gold and PGE. The geology, mineralogy, and geochemistry of the orebodies relate closely to VMS of the Cu-Zn (Cyprus) type. Fluid inclusion studies allowed an estimation of metamorphic conditions at pressures of 2/2’5 kb and T 325/350ºC. New determinations using the chlorite geothermometer yield temperatures around 320 ºC, corresponding to pressures near 2 kb according to the isochores deduced from the fluid inclusion study, although in the Barqueira mine higher temperatures, up to 350 ºC, are found, corresponding to presssures up to 2’5 kb. Pb isotopic compositions of pyrite point to a double source of Pb, i.e. a main mantle and a subordinate crustal source. The values for 87SR/86Sr in pyrite support this interpretation, but some results suggest later mobilization in an open system, corresponding to solution-transfer. Age determinations of pyrite deduced from the Pb isotope uranogenic graph, ≈ 480 Ma, do not fit with the metamorphic ages published for the Moeche Unit, and might point to the age of Pb extraction from the mantle.

Hierarchical and hybrid polymer nanocomposites based on carbon nanotubes and inorganic fullerene type nanoparticles

The influence of singlewalled carbon nanotubes (SWCNT) and inorganic fullerenelike tungsten disulfide nanoparticles (IFWS2) on the morphology and thermal, mechanical and electrical performance of multifunctional fibrereinforced polymer composites has been investigated. Significant improvements were observed in stiffness, strength and toughness in poly (ether ether ketone) (PEEK) / (SWCNT) / glass fibre (GF) laminates when a compatibilizer was used for wrapping the CNTs. Hybrid poly(phenylene sulphide) (PPS)/IFWS2/ carbon fibre (CF) reinforced polymer composites showed improved mechanical and tribological properties attributed to a synergetic effect between the IF nanoparticles and CF.

Biogas from MSW landfill: Composition and determination of chlorine content with the AOX (adsorbable organically bound halogens) technique

An exhaustive characterization of the biogas from some waste disposal facilities has been carried out. The analysis includes the main components (methane, carbon dioxide, nitrogen and oxygen) as well as trace components such as hydrogen sulphide, ammonia and VOCs (volatile organic compounds) including siloxanes and halogenated compounds. VOCs were measured by GC/MS (Gas Chromatography/Mass Spectrometry) using two different procedures: thermal desorption of the Tenax TA and Carbotrap 349 tubes and SPME (Solid Phase Micro-Extraction). A method has been established to measure the total halogen content of the biogas with the AOX (adsorbable organically bound halogens) technique. The equipment used to analyze the samples was a Total Organic Halogen Analyzer (TOX-100). Similar results were obtained when comparing the TOX (Total Organic Halogen) values with those obtained by GC/MS. The halogen content in all the samples was under 22 mg Cl/Nm3 which is below the limit of 150 mg/Nm3 proposed in the Spanish Regulations for any use of the biogas. The low chlorine content in the biogas studied, as well as the low content of other trace compounds, makes it suitable for use as a fuel for electricity generating engines.

Chemical characterization of emissions from a municipal solid waste treatment plant

Gaseous emissions are an important problem in municipal solid waste (MSW) treatment plants. The sources points of emissions considered in the present work are: fresh compost, mature compost, landfill leaks and leachate ponds. Hydrogen sulphide, ammonia and volatile organic compounds (VOCs) were analysed in the emissions from these sources. Hydrogen sulphide and ammonia were important contributors to the total emission volume. Landfill leaks are significant source points of emissions of H2S; the average concentration of H2S in biogas from the landfill leaks is around 1700 ppmv. The fresh composting site was also an important contributor of H2S to the total emission volume; its concentration varied between 3.2 and 1.7 ppmv and a decrease with time was observed. The mature composting site showed a reduction of H2S concentration (<0.1 ppmv). Leachate pond showed a low concentration of H2S (in order of ppbv). Regarding NH3, composting sites and landfill leaks are notable source points of emissions (composting sites varied around 30–600 ppmv; biogas from landfill leaks varied from 160 to 640 ppmv). Regarding VOCs, the main compounds were: limonene, p-cymene, pinene, cyclohexane, reaching concentrations around 0.2–4.3 ppmv. H2S/NH3, limonene/p-cymene, limonene/cyclohexane ratios can be useful for analysing and identifying the emission sources.

Composition of basalts from the north part of the Bougault anomaly, Mid-Atlantic Ridge 15°N

A quantitative model of development of magmatic and ore-magmatic systems under crests of mid-ocean ridges is constructed. Correct physical models of melting zone formation in approximation to active spreading, non-stationary dynamics of magma intrusion from a center of generation, filling of magma chambers of various shapes, feeding of fissure-type volcanoes, and retrograde boiling of melts during solidification of intrusive bodies beneath axial zones of spreading in crests of ridges are proposed. Physicochemical and mathematical theories of disintegration of multi-component solutions, growth of liquational drops of ore melts, and sublimation of components from magmatic gases are elaborated. Methods for constructing physically correct models of heat and mass transfer in heterophase media are devised. Modeling of development of magmatic and ore-magmatic systems on the basis of the Usov-Kuznetsov facies method and the Pospelov system approach are advanced. For quantitative models numerical circuits are developed and numerical experiments are carried out.

Chemical compositions of rocks and minerals from an underwater volcano of the Kuril deep-sea basin

Mineralogy and geochemistry of low-temperature hydrothermal manifestations occurring on the surface of basalts and in their cracks within a submarine volcano in the north-eastern part of the Kuril deep-sea basin have been studied. The following order of isolation of mineral phases has been found out: Fe-rich sulphides (pyrite) - Fe-rich layered silicates (hydromica of celadonite-nontronite type) - amorphous silica (opal) - Fe-oxyhydroxides (goethite) - Mn-oxyhydroxides (vernadite). Sulphide mineralization is of the phenocryst-stockwork type. Finding of pure barite fragments does not exclude presence of hydrothermal exhalations (smokers) on this volcanic structure.

Limitations of microbial hydrocarbon degradation at the Amon Mud Volcano (Nile Deep Sea Fan)

The Amon mud volcano (MV), located at 1250 m water depth on the Nile Deep Sea Fan, is known for its active emission of methane and non-methane hydrocarbons into the hydrosphere. Previous investigations showed a low efficiency of hydrocarbon-degrading anaerobic microbial communities inhabiting the Amon MV center in the presence of sulphate and hydrocarbons in the seeping subsurface fluids. By comparing spatial and temporal patterns of in situ biogeochemical fluxes, temperature gradients, pore water composition and microbial activities over three years, we investigated why the activity of anaerobic hydrocarbon degraders can be low despite high energy supplies. We found that the central dome of the Amon MV, as well as a lateral mud flow at its base, showed signs of recent exposure of hot subsurface muds lacking active hydrocarbon degrading communities. In these highly disturbed areas, anaerobic degradation of methane was less than 2% of the methane flux. Rather high oxygen consumption rates compared to low sulphide production suggest a faster development of more rapidly growing aerobic hydrocarbon degraders in highly disturbed areas. In contrast, the more stabilized muds surrounding the central gas and fluid conduits hosted active anaerobic hydrocarbon-degrading microbial communities. Furthermore, within three years, cell numbers and hydrocarbon degrading activity increased at the gas-seeping sites. The low microbial activity in the hydrocarbon-vented areas of Amon mud volcano is thus a consequence of kinetic limitations by heat and mud expulsion, whereas most of the outer mud volcano area is limited by hydrocarbon transport.

In situ measurements of hydrogen sulfide, oxygen, and temperature in diffuse fluids of the ultramafic-hosted Logatchev hydrothermal vent field (Mid-Atlantic Ridge)

The Logatchev hydrothermal vent field (14°45'N, Mid-Atlantic Ridge) is located in a ridge segment characterized by mantle-derived ultramafic outcrops. Compared to basalt-hosted vents, Logatchev high temperature fluids are relatively low in sulfide indicating that the diffuse, low temperature fluids of this vent field may not contain sufficient sulfide concentrations to support a chemosymbiotic invertebrate community. However, the high abundances of bathymodiolin mussels with bacterial symbionts related to free-living sulfur oxidizing bacteria suggested that bioavailable sulfide is present at Logatchev. To clarify if diffuse fluids above mussel beds of Bathymodiolus puteoserpentis provide the reductants and oxidants needed by their symbionts for aerobic sulfide oxidation, in situ microsensor measurements of dissolved hydrogen sulfide and oxygen were combined with simultaneous temperature measurements. High temporal fluctuations of all three parameters were measured above the mussel beds. H2S and O2 co-existed with mean concentrations between 9-31 µM (H2S) and 216-228 µM (O2). Temperature maxima (<= 7.4°C) were generally concurrent with H2S maxima (<= 156 µM) and O2 minima (>= 142 µM). Long-term measurements for 250 days using temperature as a proxy for oxygen and sulfide concentrations indicated that the mussels were neither oxygen- nor sulfide-limited. Our in situ measurements at Logatchev indicate that sulfide may also be bioavailable in diffuse fluids from other ultramafic-hosted vents along slow- and ultraslow-spreading ridges.

Chemical and isotopic compositions of hydrothermal manifestations and minerals from the Broken Spur hydrothermal field

A representative collection of hydrothermal manifestations was sampled practically from all hydrothermal mounds of the Broken Spur hydrothermal vent field with use of the Mir manned submersibles during three cruises of R/V Akademik Mstislav Keldysh. Mineral associations characteristic for different morphological types of sulfide ores from hydrothermal pipes, plates, and diffusers are assessed. Particular attention is paid to distribution of minor elements and their distribution patterns determined by mineralogical zonation. Measured isotopic composition of sulfur in sulfide minerals varies from 0.4 to 5.2 per mil that indicates their similarity with ores from the Snake Pit vent field and is related to dilution of hot ore-bearing solutions by seawater and reduction of water sulfate ions to H2S with heavy isotopic composition.

Chemical composition of the soluble fraction of oxidate portions of Lakes Shebadnowan ferromanganese concretions

Shebandowan Lakes, Ontario, are the site of at least 49 shallow (2-12 m) ferromanganese concretion deposits, widely distributed throughout the 48 km of the watercourse. X-ray diffraction and Mossbauer methods have revealed the presence of goethite in some of the concretions. Chemical analyses of the acid soluble portions of 72 samples gave an average composition of 43.1% Fe and 5.65% Mn with a low content of trace elements. The Shebandowan concretions are among the richest in iron of lake concretions reported, possibly because only the acid soluble portion was analysed. Their low content of trace elements suggests rapid growth rates and a relatively young age. A positive correlation was found between Mn and K, Ca, Mg, Cu, Ni, and Co and the relationship between the last three and Mn was deemed significant. Zn was independent of association with either Mn and Fe, probably due to the presence locally of zinc sulphide deposits. Analyses of lake bottom and influent waters suggested that frequent resampling of the sites would be required throughout the year to permit meaningful interpretation of the effect of water composition of concretions. Analyses of sediment cores from 20 concretion sites indicated an upward increase in Fe and Mn and in the Mn/Fe ratio, consistent with the model of upward migration of the elements, where Mn is more mobile than Fe. This study concludes that a considerable proportion of the elements have been supplied to the Shebandowan concretions via the diagenetic process; generally a minor fraction of the elements has been abstracted directly from the superjacent water.