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11.
Micro-Raman spectroscopy, even though a very promising technique, is not still routinely applied to analyse H2O in silicate glasses. The accuracy of Raman water determinations critically depends on the capability to predict and take into account both the matrix effects (bulk glass composition) and the analytical conditions on band intensities. On the other hand, micro-Fourier transform infrared spectroscopy is commonly used to measure the hydrous absorbing species (e.g., hydroxyl OH and molecular H2O) in natural glasses, but requires critical assumptions for the study of crystal-hosted glasses. Here, we quantify for the first time the matrix effect of Raman external calibration procedures for the quantification of the total H2O content (H2OT = OH + H2Om) in natural silicate glasses. The procedures are based on the calibration of either the absolute (external calibration) or scaled (parameterisation) intensity of the 3550 cm−1 band. A total of 67 mafic (basanite, basalt) and intermediate (andesite) glasses hosted in olivines, having between 0.2 and 4.8 wt% of H2O, was analysed. Our new dataset demonstrates, for given water content, the height (intensity) of Raman H2OT band depends on glass density, reflectance and water environment. Hence this matrix effect must be considered in the quantification of H2O by Raman spectroscopy irrespective of the procedure, whereas the parameterisation mainly helps to predict and verify the self-consistency of the Raman results. In addition, to validate the capability of the micro-Raman to accurately determine the H2O content of multicomponent aluminosilicate glasses, a subset of 23 glasses was analysed by both micro-Raman and micro-FTIR spectroscopy using the band at 3550 cm−1. We provide new FTIR absorptivity coefficients (ε3550) for basalt (62.80 ± 0.8 L mol−1 cm−1) and basanite (43.96 ± 0.6 L mol−1 cm−1). These values, together with an exhaustive review of literature data, confirm the non-linear decline of the FTIR absorptivity coefficient (ε3550) as the glass depolymerisation increases. We demonstrate the good agreement between micro-FTIR and micro-Raman determination of H2O in silicate glasses when the matrix effects are properly considered.  相似文献   
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The palaeontological site of Venta Micena (Orce, Andalusia, Spain) lies in the eastern sector of the Guadix–Baza basin, one of the best documented areas in Europe for Plio‐Pleistocene biostratigraphy. The combination of biochronological and palaeomagnetic results, combined with the radiometric data obtained for Atapuerca Sima del Elefante, indicated that the Venta Micena stratum was formed between the Jaramillo and Olduvai palaeomagnetic events, most likely between 1.22 and 1.77 Ma. Five fossil teeth from two outcrops (sites A and B) were selected to assess the potential of combined uranium series–electron spin resonance (US‐ESR) dating of Early Pleistocene sites. Although the US‐ESR results of the first outcrop showed a large scatter between the three teeth, the mean age of 1.37 ± 0.24 Ma can be considered a reasonable age estimate for Venta Micena. The mean ESR age of 0.62 ± 0.03 Ma obtained for site B seems to be a severe underestimation when compared with the independent age control. This underestimation is attributed to a relative recent U‐mobilization event that led to some U‐leaching. The results show that any ESR age calculations of old samples are extremely sensitive to variations in the measured 230Th/234U ratios in dental tissues. Although the results demonstrate that ESR can in principle be applied to Early Pleistocene sites, they also reveal the complexity of dating such old teeth. It is necessary to continue research in several directions, such as study of the behaviour of ESR signals in old teeth and understanding recent U‐mobilization processes, to improve the reliability of the combined US‐ESR dating method applied to Early Pleistocene times, a period for which the number of available numerical dating techniques is very limited. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   
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Many poromechanical studies of rocks give little regard to the micropetrographic observation of their constituents. The aim of this study is to show how such a detailed study can help understand and provide more precision on the poromechanical behaviour of the material. The rock studied here is an oolitic limestone. Micropetrography reveals the nature of the constituents (calcite, mostly in the form of fine‐grained micrite), their abundance, their organization (micrite organized in ooids linked by a calcitic cement, small‐sized highly connected isotropic porosity, scarce unconnected porosity) and the structure of the rock (global isotropy, small heterogeneities due to sedimentological phenomena, no microcracks). Micropetrography completes the information obtained by poromechanics in that it allows the observation of elements deduced from macroscopical tests. The aim of this paper is to show the effect of microporosity on permeability and flow in a rock where microporous grains are in contact with each other.  相似文献   
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Our understanding on how ash particles in volcanic plumes react with coexisting gases and aerosols is still rudimentary, despite the importance of these reactions in influencing the chemistry and dynamics of a plume. In this study, six samples of fine ash (<100 m) from different volcanoes were measured for their specific surface area, as, porosity and water adsorption properties with the aim to provide insights into the capacity of silicate ash particles to react with gases, including water vapour. To do so, we performed high-resolution nitrogen and water vapour adsorption/desorption experiments at 77 K and 303 K, respectively. The nitrogen data indicated as values in the range 1.1–2.1 m2/g, except in one case where a as of 10 m2/g was measured. This high value is attributed to incorporation of hydrothermal phases, such as clay minerals, in the ash surface composition. The data also revealed that the ash samples are essentially non-porous, or have a porosity dominated by macropores with widths >500 Å. All the specimens had similar pore size distributions, with a small peak centered around 50 Å. These findings suggest that fine ash particles have relatively undifferentiated surface textures, irrespective of the chemical composition and eruption type. Adsorption isotherms for water vapour revealed that the capacity of the ash samples for water adsorption is systematically larger than predicted from the nitrogen adsorption as values. Enhanced reactivity of the ash surface towards water may result from (i) hydration of bulk ash constituents; (ii) hydration of surface compounds; and/or (iii) hydroxylation of the surface of the ash. The later mechanism may lead to irreversible retention of water. Based on these experiments, we predict that volcanic ash is covered by a complete monolayer of water under ambient atmospheric conditions. In addition, capillary condensation within ash pores should allow for deposition of condensed water on to ash particles before water reaches saturation in the plume. The total mass of water vapour retained by 1 g of fine ash at 0.95 relative water vapour pressure is calculated to be ~10–2 g. Some volcanic implications of this study are discussed.Editorial responsibility: J. Gilbert  相似文献   
17.
The effectiveness of fertilizers for crude oil bioremediation in sub-Antarctic intertidal sediments was tested over a one-year period in a series of ten (10) experimental enclosures. Chemical, microbial and toxicological parameters demonstrated the effectiveness of various fertilizers in a pristine environment where hydrocarbon degrading bacteria (HDB) had not been stimulated by previous accidental spills or human activities. The low temperature of seawater (3-4 degrees C) had no obvious effects on the HDB community and the bioremediation process. Over 90% of n-alkanes were degraded in the first six months and most light aromatics (2-3 rings) disappeared during the first year of observation. The toxicity of oiled residues (Microtox(R) SP) was significantly reduced in the first 6 months of the process, but it increased again in the last months of the experiment. One of the fertilizers containing fishbone compost enriched with urea, inorganic phosphorus and a lipidic surfactant reduced significantly the toxicity of oil residues in the last 3 months of the experiment. Interstitial waters collected below the oil slicks during the remediation showed no toxicity, and even stimulated Vibrio fischeri. When comparing all fertilizers to the control plots, a good correlation (r(2)=0.82) was found between the growth rate of HDB and the degradation rate of n-alkanes in the first 90 days of the experiment only indicating that fertilizers were efficient for at least 3 months but their beneficial effects were lost after 6 months.  相似文献   
18.
As part of the Canadian contribution to the International Polar Year (IPY), several major international research programs have focused on offshore arctic marine ecosystems. The general goal of these projects was to improve our understanding of how the response of arctic marine ecosystems to climate warming will alter food web structure and ecosystem services provided to Northerners. At least four key findings from these projects relating to arctic heterotrophic food web, pelagic-benthic coupling and biodiversity have emerged: (1) Contrary to a long-standing paradigm of dormant ecosystems during the long arctic winter, major food web components showed relatively high level of winter activity, well before the spring release of ice algae and subsequent phytoplankton bloom. Such phenological plasticity among key secondary producers like zooplankton may thus narrow the risks of extreme mismatch between primary production and secondary production in an increasingly variable arctic environment. (2) Tight pelagic-benthic coupling and consequent recycling of nutrients at the seafloor characterize specific regions of the Canadian Arctic, such as the North Water polynya and Lancaster Sound. The latter constitute hot spots of benthic ecosystem functioning compared to regions where zooplankton-mediated processes weaken the pelagic-benthic coupling. (3) In contrast with another widely shared assumption of lower biodiversity, arctic marine biodiversity is comparable to that reported off Atlantic and Pacific coasts of Canada, albeit threatened by the potential colonization of subarctic species. (4) The rapid decrease of summer sea-ice cover allows increasing numbers of killer whales to use the Canadian High Arctic as a hunting ground. The stronger presence of this species, bound to become a new apex predator of arctic seas, will likely affect populations of endemic arctic marine mammals such as the narwhal, bowhead, and beluga whales.  相似文献   
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BIOSCREEN is a well‐known simple tool for evaluating the transport of dissolved contaminants in groundwater, ideal for rapid screening and teaching. This work extends the BIOSCREEN model for the calculation of stable isotope ratios in contaminants. A three‐dimensional exact solution of the reactive transport from a patch source, accounting for fractionation by first‐order decay and/or sorption, is used. The results match those from a previously published isotope model but are much simpler to obtain. Two different isotopes may be computed, and dual isotope plots can be viewed. The dual isotope assessment is a rapidly emerging new approach for identifying process mechanisms in aquifers. Furthermore, deviations of isotope ratios at specific reactive positions with respect to “bulk” ratios in the whole compound can be simulated. This model is named BIOSCREEN‐AT‐ISO and will be downloadable from the journal homepage.  相似文献   
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