Protracted fluid-induced melting during Barrovian metamorphism in the Central Alps

The timing and dynamics of fluid-induced melting in the typical Barrovian sequence of the Central Alps has been investigated using zircon chronology and trace element composition. Multiple zircon domains in leucosomes and country rocks yield U–Pb ages spanning from ~32 to 22 Ma. The zircon formed during Alpine melting can be distinguished from the inherited and detrital cores on the basis of their age, Th/U (<0.1) and trace element composition. Ti-in-zircon thermometry indicates crystallization temperatures around 620–700°C. Their composition allows discriminating between (1) zircon formation in the presence of early garnet, (2) zircon in equilibrium with abundant L-MREE-rich accessory phases (allanite, titanite and apatite) typical of metatonalites, and (3) zircon formed during melting of metasediments in feldspar-dominated assemblages. The distribution of zircon overgrowths and ages indicate that repeated melting events occurred within a single Barrovian metamorphic cycle at roughly constant temperature; that in the country rocks zircon formation was limited to the initial stages of melting, whereas further melting concentrated in the segregated leucosomes; that melting occurred at different times in samples a few meters apart because of the local rock composition and localized influx of the fluids; and that leucosomes were repeatedly melted when fluids became available. The geochronological data force a revision of the temperature–time path of the migmatite belt in the Central Alps. Protracted melting over 10 My followed the fast exhumation of Alpine eclogites contained within the same region and preceded fast cooling in the order of 100°C/Ma to upper crustal levels.     

Automobile Emissions of Acetonitrile: Assessment of its Contribution to the Global Source

Based on an estimated global fuel consumption of 2.57 × 10¹⁵g(C) y^–1 and the assumption thatthe fossil fuel burned in Austria is globallyrepresentative, an upper limit of 0.021 (+150%, –50%)Tg y^–1 for global CH₃CN emission dueto fossil fuel burning was obtained from the relativeenhancement of the concentrations of toluene, benzene,and acetonitrile (methyl cyanide) during strong,short-term traffic pollution. This is less than 6% ofthe total global budget of CH₃CN, which is dominatedby an emission rate of 0.8 Tg y^–1 from biomassburning.     

Beitrag zur Kenntnis der Blaualgenvegetation der Thermen von Baden und Leukerbad (Schweiz)

Ohne Zusammenfassung     

Clay catalysis of aromatic hydrogen-exchange reactions

The exchange of aromatic hydrogen in the presence of clay catalysts has been studied by measuring the rates of detritiation of some tritiated naphthalene derivatives on homoionic bentonites. The rate of reaction is influenced by the position of tritium on the ring, the presence of a methoxysubstituent on the ring and the acidity of the clay catalyst. It is inferred that the mechanism of exchange involves an adsorbed species similar to the arenium ion intermediate of electrophilic aromatic substitutions in homogeneous systems. In some cases exchange of hydrogen between acidic clay surfaces and naphthalene derivatives could be detected at temperatures as low as 23°C, and in aqueous slurries at 70°C. This observed reactivity suggests that these reactions could occur in sedimentary environments where organic matter, such as petroleum hydrocarbons, is in contact with clay surfaces. The hydrogen isotopic composition of aromatic hydrogen in petroleum may therefore be related to that of the acidic water adsorbed on clay surfaces with which the petroleum has been in contact.     

Acid catalysis of alkyl hydrogen exchange and configurational isomerisation reactions: acyclic isoprenoid acids

Acid-catalysed alkyl hydrogen exchange and configurational isomerisation has been studied in a series of acyclic isoprenoid acids when they were heated at 160°C in the presence of a montmorillonite. Hydrogen exchange occurred between the adsorbed water of the clay surface and the a position of the isoprenoid acids. In cases where this position was chiral, exchange was accompanied by configurational isomerisation. Configurational isomerisation occurred more slowly in experiments conducted without a clay matrix in the presence of water. These results have been rationalized in terms of a reaction mechanism involving protonation of the carbonyl oxygen causing enolization and consequent hydrogen exchange at the a position of the acids. This mechanism was used to account for the relatively fast rate of isomerisation of C-2 chiral centres in sedimentary acyclic isoprenoid acids during maturation.     

Incorporation of aerosol particles between 25 and 850 nm into cloud elements: measurements with a new complementary sampling system

The interpretation of the physico-chemical processes in clouds is facilitated by segregating in situ cloud elements from their carrier gas and small particles (interstitial aerosol). Thus, the present study focuses on the quantitative phase segregation of interstitial air from cloud phase by two complementary samplers with microphysical on-line analysis of the separated phases. An improved counterflow virtual impactor (CVI) was developed for the collection and subsequent evaporation of the condensed phase, releasing dissolved gaseous material and residual particles. This sampler operates in the size range of few micrometers up to 50 μm in cloud element diameter and is matched by an interstitial Round Jet Impactor sampling the gas phase with interstitial particles. Calibrations of both samplers verified the calculated cut sizes D₅₀ of 4, 5, and 6 μm and quantified the slope of the collection efficiency curves. Until this study no direct CVI measurements of the residual particle sizes far below the diameter of 0.1 μm were available. For the first time a CVI was connected to a Differential Mobility Particle Sizer (DMPS) scanning between 25 nm and 850 nm, thus, including the entire Aitken mode in the residual size analysis. Cloud studies on the Puy de Dôme, France, revealed residual particle sizes including Aitken mode (diameter D<100 nm) and accumulation mode (D>100 nm). A major feature of the CVI data is expressed by the fact that despite incomplete incorporation of accumulation mode particles in cloud elements there are contributions of particles with diameters smaller than 0.1 μm to the number of residual particles. Cloud entrainment from height levels above the maximum supersaturation as wells as the size-dependent chemical composition of the aerosol population most likely produced the S-shaped size-dependent partitioning of residual particles. Compared to earlier studies the 50% partitioning diameters dropped significantly below 100 nm to roughly 70 nm.     

Experimental study of gas hydrate formation and destabilisation using a novel high-pressure apparatus

A novel variable-volume type high-pressure apparatus has been designed, constructed and used for gas hydrate investigations. The apparatus has an operating temperature ranging from 253 K to 473 K and pressure ranging from 0.1 MPa to 60 MPa. Its central component consists of a viewing windows cell to which several sensors or analytical instruments can be connected. At its present configuration, a Raman spectrometer and a gas chromatograph are connected for the study of the liquid (or solid) and the gas phases respectively.     

Internal Differentiation of the Archean Continental Crust: Fluid-Controlled Partial Melting of Granulites and TTG-Amphibolite Associations in Central Finland

Fault bound blocks of granulite and enderbite occur within upperamphibolite-facies migmatitic tonalitic–trondhjemitic–granodioritic(TTG) gneisses of the Iisalmi block of Central Finland. Theseunits record reworking and partial melting of different levelsof the Archean crust during a major tectonothermal event at2·6–2·7 Ga. Anhydrous mineral assemblagesand tonalitic melts in the granulites formed as a result ofhydrous phase breakdown melting reactions involving amphiboleat peak metamorphic conditions of 8–11 kbar and 750–900°C.A nominally fluid-absent melting regime in the granulites issupported by the presence of carbonic fluid inclusions. Thegeochemical signature of light rare earth element (LREE)-depletedmafic granulites can be modelled by 10–30 wt % partialmelting of an amphibolite source rock leaving a garnet-bearingresidue. The degree of melting in intermediate granulites isinferred to be less than 10 wt % and was restricted by the availabilityof quartz. Pressure–temperature estimates for the TTGgneisses are significantly lower than for the granulites at660–770°C and 5–6 kbar. Based on the P–Tconditions, melting of the TTG gneisses is inferred to haveoccurred at the wet solidus in the presence of an H₂O-rich fluid.A hydrous mineralogy, abundant aqueous fluid inclusions andthe absence of carbonic inclusions in the gneisses are in accordancewith a water-fluxed melting regime. Low REE contents and strongpositive Eu anomalies in most leucosomes irrespective of thehost rock composition suggest that the leucosomes are not meltcompositions, but represent plagioclase–quartz assemblagesthat crystallized early from felsic melts. Furthermore, similarplagioclase compositions in leucosomes and adjacent mesosomesare not a ‘migmatite paradox’, as both record equilibrationwith the same melt phase percolating along grain boundaries. KEY WORDS: Archean continental crust; fluid inclusion; granulite; migmatite; partial melting