Climatic oscillations in central Italy during the Last Glacial–Holocene transition: the record from Lake Accesa

This paper presents an event stratigraphy based on data documenting the history of vegetation cover, lake‐level changes and fire frequency, as well as volcanic eruptions, over the Last Glacial–early Holocene transition from a terrestrial sediment sequence recovered at Lake Accesa in Tuscany (north‐central Italy). On the basis of an age–depth model inferred from 13 radiocarbon dates and six tephra horizons, the Oldest Dryas–Bølling warming event was dated to ca. 14 560 cal. yr BP and the Younger Dryas event to ca. 12 700–11 650 cal. yr BP. Four sub‐millennial scale cooling phases were recognised from pollen data at ca. 14 300–14 200, 13 900–13 700, 13 400–13 100 and 11 350–11 150 cal. yr BP. The last three may be Mediterranean equivalents to the Older Dryas (GI‐1d), Intra‐Allerød (GI‐1b) and Preboreal Oscillation (PBO) cooling events defined from the GRIP ice‐core and indicate strong climatic linkages between the North Atlantic and Mediterranean areas during the last Termination. The first may correspond to Intra‐Bølling cold oscillations registered by various palaeoclimatic records in the North Atlantic region. The lake‐level record shows that the sub‐millennial scale climatic oscillations which punctuated the last deglaciation were associated in central Italy with different successive patterns of hydrological changes from the Bølling warming to the 8.2 ka cold reversal. Copyright © 2006 John Wiley & Sons, Ltd.     

Disproportionation of Fe<Superscript>2+</Superscript> in Al-free silicate perovskite in the laser heated diamond anvil cell as recorded by electron probe microanalysis of oxygen

Experimental evidence is reported for Fe²⁺ disproportionation in Al-free perovskite (Pv), when submitted to large temperature gradients (i.e., under off-equilibrium conditions) in a laser heated diamond anvil cell (LHDAC). To enable this effect, the experimental procedure was designed to produce large radial and axial temperature gradients. In the Pv and ferropericlase (Fp) assemblage synthesized after dissociation of natural olivine, the three chemical states of iron (i.e., Fe⁰, Fe²⁺ and Fe³⁺) could be evidenced by electron probe microanalysis (EPMA), through variations of oxygen contents attached to the Fe cations. Despite inherent difficulties for determination of O-contents and Fe³⁺/ΣFe ratios using EPMA, we recorded significant changes in iron oxidation state across the laser-heated strip. These changes are correlated with variations in composition for the major elements (Fe, Mg, and Si), which evidences that the Pv/Fp assemblage experienced large segregation under the strong temperature gradients. Grains of metallic iron were detected in parts of the laser-heated strip coexisting with a Pv phase with Fe/(Mg + Fe) = 6 at% and most of its iron as Fe³⁺. This Fe²⁺-disproportionation reaction involves insertion of Fe³⁺-defects in the Pv lattice. This Fe³⁺-bearing Pv phase is presumably unstable and decomposes into a mineral assemblage including magnesioferrite, which is detected at the border of the laser-heated strip.     

Experimental reduction of aqueous sulphate by hydrogen under hydrothermal conditions: Implication for the nuclear waste storage

Sulphate reduction by hydrogen, likely to occur in deep geological nuclear waste storage sites, was studied experimentally in a two-phase system (water + gas) at 250-300 °C and under 4-16 bars H₂ partial pressure in hydrothermal-vessels. The calculated activation energy is 131 kJ/mol and the half-life of aqueous sulphate in the presence of hydrogen and elemental sulphur ranges from 210,000 to 2.7 × 10⁹ years at respective temperatures of 90 °C, the thermal peak in the site and 25 °C, the ambient temperature far from the site. The features and rate of the sulphate reduction by H₂ are close to those established for TSR in oil fields. The experiments also show that the rate of sulphate reduction is not significantly affected in the H₂ pressure range of 4-16 bars and in the pH range of 2-5, whereas a strong increase is measured at pH below 2. We suggest that the condition for the reaction to occur is the speciation of sulphate dominated by non symmetric species ( at low pH), and we propose a three steps reaction, one for each intermediate-valence sulphur species, the first one requiring H₂S as electron donor rather than H₂. We distinguish two possible reaction pathways for the first step, depending on pH: reduction of sulphate into sulphur dioxide below pH 2 or into thiosulphate or sulphite + elemental sulphur in the pH range 2-5.     

New experimental constraints on the composition and structure of tholins

Powdered samples of carbon-nitrogen-hydrogen “tholins” that mimic Titan's atmosphere aerosols were produced under levitation conditions in the laboratory with a dusty plasma (PAMPRE experiment) using different initial N₂:CH₄ gas mixtures and studied using UV Raman and infrared spectroscopy, X-ray diffraction and high resolution transmission electron microscopy (HRTEM). Comparison between the tholins produced in the PAMPRE experiments and samples prepared by other techniques reveal that they form a fairly homogeneous family of hydrogenated carbon nitride materials. Wall effects during the PAMPRE deposition experiments and other were found to have little effect on the chemical structure of tholins. The first-order UV Raman bands of the disordered carbonaceous materials point to a large contribution of sp² clusters present compared with olefinic CN or CC groupings, whereas features at 690 and 980 cm⁻¹ suggest C₃N₃ rings are present as a species inserted in the macromolecular network. Diffraction techniques do not indicate the presence of large polyaromatic species in any of the tholins studied, whatever their nitrogen concentration, in disagreement with certain previous observations. This precludes the idea that the nature and degree of absorption in the visible range is controlled by the size of polyaromatic species, as has been observed in series of carbon-based materials obtained via thermal processing. Infrared spectroscopy analysis of the tholins has confirmed earlier identifications of chemical groups present including primary amines, nitriles, and alkyl moieties such as CH₂/CH₃, but has ruled out CH₂/CH₃ branches appearing on secondary or tertiary amines. Similar analyses were also performed on a polymeric (HCN)_x material, which was found to present several similarities with the tholins, hence suggesting similar polymerization processes.     

Phylogenetic,histological and age determination for investigation of non-native tropical black-lip pearl oyster, <Emphasis Type="Italic">Pinctada margaritifera</Emphasis>, settled in jeju,Korea

This study reports the first finding of tropical blacklip pearl (BLP) oyster, Pinctada margaritifera, in Korean waters. One BLP oyster was found and sampled from Beom-seom islet (33°13′N, 126°33′E) in the southern coast of Jeju Island, Korea in February, 2011. The taxonomic status of the specimen was confirmed by nucleotide sequences of the mitochondrial gene cytochrome oxidase I and 28S ribosomal DNA. Oxygen isotopic analysis (δ¹⁸O_sh) and histology were used to determine the specimen’s age and reproductive stage, which were 3.5 years and ripe male, respectively. This BLP oyster most likely originated in an area in the subtropics or tropics, such as the Okinawa archipelagic or Micronesian regions. We suggest that intensive monitoring surveys are necessary for confirming the northward expansion of BLP oyster in Korean waters in the near future.     

Spatio-temporal fragmentation of leisure activities in information era: Empirical evidence from Nanjing,China

Activity fragmentation provides a new approach for understanding the transformation of urban space and function in the information era. Numerous theoretical and empirical studies have been conducted on activity fragmentation, but few studies have focused on the fragmentation of leisure activities. This study was intended to extend the extant literature by: 1) analysing the spatio-temporal fragmentation of physical and virtual leisure activities by using a dataset collected in Nanjing, China, and 2) evaluating the reasons of leisure activity fragmentation, as well as the potential spatial effect of activity fragmentation. The results indicated that virtual leisure activities are more fragmented than physical leisure activities, but the fragmentation of physical and virtual leisure activities varies on weekday and weekend, as well as in various locations and urban districts. In addition, the results suggested that sociodemographic factors and information and communication technology (ICT) variables distinctly affect the fragmentation of leisure activities. Meanwhile, the fragmentation of virtual leisure activities may enhance the transformation of traditional urban space by reallocating leisure activity times and locations.     

Does sediment resuspension by storms affect the fate of polychlorobiphenyls (PCBs) in the benthic food chain? Interactions between changes in POM characteristics, adsorption and absorption by the mussel Mytilus galloprovincialis

Environmental parameters and gross sedimentation rates (GSR) were monitored at a fixed site located in the Bay of Banyuls-sur-Mer (NW Mediterranean), between March 1997 and April 1998, together with the main biochemical characteristics of both sedimenting and sedimented particulate organic matter (POM). Three storms which occurred during this time period resulted in natural sediment resuspension. This is indicated by the corresponding increase in GSR and a decrease in the enzymatically hydrolysable amino acids/totally hydrolysable amino acids ratio (EHAA/THAA), within the sedimenting POM. Only the strongest storm resulted in (1) a transitory increase in fine-grained particles, (2) concomitant increases in organic carbon, carbohydrates, lipids and THAA, and (3) a decrease in the EHAA/THAA ratio in surficial sediments. For most of the assayed parameters, the values recorded after the December 1997 storm corresponded to extremes for the whole period under study. This emphasises the role of storms in controlling the characteristics of sedimented and sedimenting POM.Ten sediment types, with contrasting biochemical characteristics, were selected for experiments; these were based on the results of the monitoring survey and were used during adsorption and absorption experiments involving ¹⁴C tetrachlorobiphenyl (TCB). Adsorption rates differed significantly between the sediment types, but did not correlate with any of the assayed biochemical parameters. Absorption efficiency by the mussel Mytilus galloprovincialis also differed between the sediment types; it correlated positively with all the assayed biochemical parameters, except lipids. Comparison between the magnitudes of the increase in GSR, together with the decrease in absorption efficiency during resuspension events, suggests that resuspension tends to enhance the transfer of organic pollutants in the benthic food chain.