Structural control over equilibrium silicon and oxygen isotopic fractionation: A first-principles density-functional theory study

Isotopic fractionation factors for oxygen and silicon in selected silicates (quartz, enstatite, forsterite, lizardite, kaolinite) are calculated using first-principles methods based on density-functional theory. Good agreement between theory and experiment is found in the case of oxygen. In the case of silicon, agreement and differences with existing estimates of equilibrium fractionation factors are discussed. The relationship between silicon and oxygen fractionation factors, silicate polymerization degree and chemical composition is studied and compared with previous semi-empirical models.     

Polycyclic aromatic hydrocarbons (PAHs) in a large South American industrial coastal area (Santos Estuary, Southeastern Brazil): sources and depositional history

Located in southeastern Brazil, the Santos Estuary has the most important industrial and urban population area of South America. Since the 1950's, increased urbanization and industrialization near the estuary margins has caused the degradation of mangroves and has increased the discharge of sewage and industrial effluents. The main objectives of this work were to determine the concentrations and sources of polycyclic aromatic hydrocarbons (PAHs) in sediment cores in order to investigate the input of these substances in the last 50 years. The PAHs analyses indicated multiple sources of these compounds (oil and pyrolitic origin), basically anthropogenic contributions from biomass, coal and fossil fuels combustion. The distribution of PAHs in the cores was associated with the formation and development of Cubat?o industrial complex and the Santos harbour, waste disposal, world oil crisis and the pollution control program, which results in the decrease of organic pollutants input in this area.     

Peierls dislocation modelling in perovskite (CaTiO<Subscript>3</Subscript>): comparison with tausonite (SrTiO<Subscript>3</Subscript>) and MgSiO<Subscript>3</Subscript> perovskite

We present here a numerical modelling study of dislocations in perovskite CaTiO₃. The dislocation core structures and properties are calculated through the Peierls–Nabarro model using the generalized stacking fault (GSF) results as a starting model. The GSF are determined from first-principles calculations using the VASP code. The dislocation properties such as collinear, planar core spreading and Peierls stresses are determined for the following slip systems: [100](010), [100](001), [010](100), [010](001), [001](100), [001](010), and All dislocations exhibit lattice friction, but glide appears to be easier for [100](010) and [010](100). [001](010) and [001](100) exhibit collinear dissociation. Comparing Peierls stresses among tausonite (SrTiO₃), perovskite (CaTiO₃) and MgSiO₃ perovskite demonstrates the strong influence of orthorhombic distortions on lattice friction. However, and despite some quantitative differences, CaTiO₃ appears to be a satisfactory analogue material for MgSiO₃ perovskite as far as dislocation glide is concerned.     

Low calcification rates and calcium carbonate production in Porites panamensis at its northernmost geographic distribution

Porites panamensis is a hermatypic coral present in the eastern Pacific Ocean. Skeletal growth parameters have been reported, but studies of the relationship between annual calcification rates and environmental controls are scarce. In this study, we investigated three aspects of the annual calcification rates of P. panamensis: growth parameters among three P. panamensis populations; the sea surface temperature as a calcification rate control spanning a latitudinal gradient; and calcium carbonate production among three sites. Growth parameters varied among the sites due to the colony growth form. Massive colonies in the north showed a higher calcification rate than encrusting colonies in the south (mean: 1.22–0.49 g CaCO₃ · cm^?2 · yr^?1), where variations in calcification rates were related to growth rate (0.91–0.38 cm · yr^?1) rather than to skeletal density differences (overall mean ± SD, 1.31 ± 0.04 g CaCO₃ · cm^?3). Our results showed a positive linear relationship between annual calcification rates and sea surface temperatures within these P. panamensis populations. Differences were related to distinct oceanographic environments (within and at the entrance of the Gulf of California) with different sea surface temperature regimes and other chemical properties. Different populations calcified under different environmental conditions. Calcium carbonate production was dependent upon the calcification rate and coral cover and so carbonate production was higher in the north (coral cover 12%) than in the south (coral cover 3.5). Thus, the studied sites showed low calcium carbonate production (0.25–0.43 kg CaCO₃ · m^?2 · yr^?1). Our results showed reduced calcification rates, regional temperature regime control over calcification rates, different growth forms, low coral cover and low calcium carbonate production rates in P. panamensis.     

Zircon geochronology and geochemistry to constrain the youngest eruption events and magma evolution of the Mid-Miocene ignimbrite flare-up in the Pannonian Basin,eastern central Europe

A silicic ignimbrite flare-up episode occurred in the Pannonian Basin during the Miocene, coeval with the syn-extensional period in the region. It produced important correlation horizons in the regional stratigraphy; however, they lacked precise and accurate geochronology. Here, we used U–Pb (LA-ICP-MS and ID-TIMS) and (U–Th)/He dating of zircons to determine the eruption ages of the youngest stage of this volcanic activity and constrain the longevity of the magma storage in crustal reservoirs. Reliability of the U–Pb data is supported by (U–Th)/He zircon dating and magnetostratigraphic constraints. We distinguish four eruptive phases from 15.9 ± 0.3 to 14.1 ± 0.3 Ma, each of which possibly includes multiple eruptive events. Among these, at least two large volume eruptions (>10 km³) occurred at 14.8 ± 0.3 Ma (Demjén ignimbrite) and 14.1 ± 0.3 Ma (Harsány ignimbrite). The in situ U–Pb zircon dating shows wide age ranges (up to 700 kyr) in most of the crystal-poor pyroclastic units, containing few to no xenocrysts, which implies efficient recycling of antecrysts. We propose that long-lived silicic magma reservoirs, mostly kept as high-crystallinity mushes, have existed in the Pannonian Basin during the 16–14 Ma period. Small but significant differences in zircon, bulk rock and glass shard composition among units suggest the presence of spatially separated reservoirs, sometimes existing contemporaneously. Our results also better constrain the time frame of the main tectonic events that occurred in the Northern Pannonian Basin: We refined the upper temporal boundary (15 Ma) of the youngest counterclockwise block rotation and the beginning of a new deformation phase, which structurally characterized the onset of the youngest volcanic and sedimentary phase.     

Evidence for delayed poleward expansion of North Atlantic surface waters during the last interglacial (MIS 5e)

The Last Interglacial (Marine Isotopic Stage or MIS 5e) surface ocean heat flux from the Rockall Basin (NE Atlantic) towards the Arctic Ocean was reconstructed by analysing dinoflagellate cyst (dinocyst) assemblages in four sediment cores. Together with records of stable isotopes and ice-rafted detritus, the assemblage data reflect the northward retreat of ice(berg)-laden waters and the gradual development towards interglacial conditions at the transition from the Saalian deglaciation (Termination II) into MIS 5e. At the Rockall Basin, this onset of the Last Interglacial is soon followed by the appearance of the thermophilic dinocyst species Spiniferites mirabilis, with relative abundances higher than those observed at present in the area. North of the Iceland-Scotland Ridge, however, S. mirabilis only appears in significant numbers during late MIS 5e, between ～118 and 116.5 ka. Hence, fully marine Last Interglacial conditions with most intense Atlantic surface water influence occurred during late MIS 5e in the Nordic seas, and consequently also farther north in the Arctic Ocean, and at times when northern hemisphere summer insolation was already significantly decreased. The stratigraphic position of this Late Interglacial optimum is supported by planktic foraminifers and contrasts with the timing of the early Holocene climatic optimum in this area. We interpret the delayed northward expansion of Atlantic waters towards the polar latitudes as a result of the Saalian ice sheet deglaciation and its specific impact on the subsequent water mass evolution in this region.     

Uncertainties in European summer precipitation changes: role of large scale circulation

Climate models suggest that anthropogenic emissions are likely to induce an important drying during summer over most of Europe in the late 21st century. However, the amplitude of the associated decrease in precipitation strongly varies among the different climate models. In order to reduce this spread, it is first necessary to identify its causes and the associated physical mechanisms. Consequently, the focus of this paper is to better estimate the role of large scale circulation (LSC) in precipitation changes over Europe using a multi-model framework and then to characterize the LSC changes using the weather regime paradigm. We show that LSC changes directly lead to a decrease of precipitation over northwestern Europe. This circulation-driven decrease in rainfall is mainly linked to an increase (decrease) of the occurrence of positive (negative) phase of the North Atlantic Oscillation regime. LSC is also responsible for a significant part of the models spread in precipitation changes over these regions. Over southern Europe, the role of LSC changes on multi-model mean precipitation changes is generally weak. We also show that the precipitation anomalies directly induced by LSC modifications seem to be further amplified through local feedbacks.     

The Second International Conference on the Mediterranean Coastal Environment Medcoast 95

The Second International Conference on the Mediterranean Coastal Environment Medcoast 95     

SEM-EDX Characterisation of Tropospheric Aerosols in the Negev Desert (Israel)

Individual aerosol particles collected in the Negev desert in Israel during a summer and winter campaign in 1996–1997 were analysed by scanning electron microscopy with energy-dispersive X-ray analysis. Hierarchical cluster analysis was performed to interpret the data on the basis of particle diameter and composition. Eleven particle classes (groups) provided clues on sources and/or particle formation. The summer samples were enriched in sulphates and mineral dusts; the winter samples contained more sea salts, aged sea salts, and industrial particles. The fine size fraction below 1 m diameter was enriched in secondary particles and showed evidence of atmospheric processing. The secondary sulphate particles were mainly attributed to long-range transport. A regional conversion from calcite to calcium sulphate occurred during summer. Industrial particles originating from local pollution appeared during winter.