Osmium-strontium-neodymium-lead isotopic covariations in mid-ocean ridge basalt glasses and the heterogeneity of the upper mantle

Osmium, strontium, neodymium, and lead isotopic data have been obtained for 30 hand picked samples of basaltic glass from the Pacific, Atlantic and Indian mid-oceanic ridges. Large variations in Os isotopic ratios exist in the glasses, from abyssal peridotite-like values to radiogenic compositions similar to oceanic island basalts (¹⁸⁷Os/¹⁸⁶Os and ¹⁸⁷Os/¹⁸⁸Os ratios range from 1.06 to 1.36 and from 0.128 to 0.163, respectively). Os isotopic and elemental data suggest the existence of mixing correlations. This relationship might be ascribed to secondary contamination processes; however, such a hypothesis cannot account for the negative correlation observed between Os and Nd isotopes and the existence of complementary covariations between Os and SrPb isotopes. In this case, OsSrNdPb isotopic variations are unrelated to late post-eruption or shallow level contamination. These relationships provide strong evidence that the Os isotopic composition of the samples are derived from the mantle and thus implies a global chemical heterogeneity of the oceanic upper mantle. The results are consistent with the presence of recycled oceanic crust in the mantle sources of mid-ocean ridge basalts, and indicate that the unique composition of the upper mantle below the Indian ocean results from its contamination by a mantle component characterized by radiogenic Os and particularly unradiogenic Nd and Pb isotopic compositions.     

Application of trichloroacetic acid (TCA) to extraction of soft body for the determination of tissue Cd, Cu, Pb and Zn in the prosobranch Hydrobia ulvae (Pennant)

The application of trichloroacetic acid (TCA) as a shell extractant for preparation of soft body parts with reference to tissue metal concentrations (Cd, Cu, Pb, Zn) in shellfish has been evaluated on the example of the mud snail Hydrobia ulvae, a small marine prosobranch densely present in rocky and soft-bottom habitats of the eastern Atlantic. A solution of 0.1 M TCA was tested on individuals treated according to two different protocols: (1) thawed after freezing ("non-dried") and (2) thawed and air-dried to a constant weight ("dried"). Two points were investigated in detail to improve the method: individual soft tissue dry weight and tissue metal concentration following a standard digestion method. In both instances, the results were compared with those from manually dissected snails. Conditions for total shell decalcification of 60 individuals (3-4 mm long) were 5.5 h in 20 ml of 0.1 M TCA.No differences in individual soft tissue weight were observed between the treatments, indicating good efficiency of the TCA extraction with respect to weight of soft body parts. In contrast, tissue metal concentrations varied among treatments. The TCA extraction of the dried animals had a good recovery for Cd, most likely due to the lower solubility of Cd vital cellular components (proteins and mineral concretions) from the dried tissue. Satisfactory recoveries of the tissue concentrations of Cu and Pb were obtained for the non-dried individuals. This might be related to the specific distribution of metals in the organism (namely in the digestive glands and gonads) and their different chemical reactivity with TCA after the tissue was dried. Limited susceptibility of Zn-bearing protein bindings to complexing with TCA also accounts for significantly lower concentrations of Zn in the mud snail's soft tissue that was extracted. The 0.1 M TCA solution is therefore recommended for extraction of the shells of Hydrobia ulvae for tissue determination of Cd, Cu and Pb; however the treatment protocol does affect metal recovery and thus a consistent procedure should be followed.The extracted metals from the soft tissues and shells of the mud snails (on the basis of both metal concentrations and contents) were ranked in order of increasing contribution of soft body parts to the total (shell+tissue): Pb相似文献   

Surface area, porosity and water adsorption properties of fine volcanic ash particles

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, a_s, 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 a_s values in the range 1.1–2.1 m²/g, except in one case where a a_s 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 a_s 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     

Effects of 12 years' operation of a sewage treatment plant on trace metal occurrence within a Mediterranean commercial sponge (Spongia officinalis, Demospongiae)

The present field study uses Spongia officinalis for assessing trace metals occurrence in time and space within Mediterranean rocky communities. Nine sites were selected in the Marseille area for studying spatial trends in 12 metal concentrations. Long term changes in 8 metal concentrations were assessed at sites that had been sampled before and 12 years after the opening of a treatment plant. Spongia officinalis highly concentrated all the trace metal surveyed excepted Hg and Cd. The overall contamination level registered provided a classification of the study sites which is congruent with that given by other studies on pollutant accumulation in neighbouring sandy-bottoms or benthic assemblages. Among the metals studied, Fe, Pb, Cr are those that best highlighted a pollution gradient. In the present study, only Cd concentration did not vary in space. Except for Ni, all pollutant concentrations clearly decreased between 1984 and 1999. This very impressive decrease in heavy metal concentrations within the Marseille area represents an indisputable evidence of the improvement of the seawater quality resulting from 12 years' operation of the Marseille sewage plant. Moreover, the significant decrease also recorded in the reference population at Port-Cros might reflect an overall improvement in the seawater quality of the NW Mediterranean.     

Laboratory study of the rates and products of the phototransformations of naphthalene adsorbed on samples of titanium dioxide,ferric oxide,muscovite, and fly ash

The photodegradation of naphthalene (NPH), chosen as a model of polynuclear aromatic pollutants, has been studied in the presence of a layer of four water-insoluble inorganic solids which can be found in the troposphere (TiO₂, Fe₂O₃, muscovite, and a fly ash sample). Direct photolysis of NPH is negligible at >340 nm. Dark adsorption of NPH on TiO₂ (mainly anatase, nonporous, 50 m² g^–1) at 293 K corresponds to a surface coverage ofca. 50% at equilibrium. Under these conditions (saturated surface), the stationary-state photocatalytic degradation reaches 0.4 molecule nm^–2 h^–1 (>340 nm, radiant fluxca. 22 mW cm^–2). Dioxygen is required and its partial pressure in air is such that the degradation is zero order in O₂. Water vapor markedly increases the rate. The other particulates have also an effect, less important than that of TiO₂, however quite noticeable with respect to surface area unit for the fly ash sample which contains 3.2% Fe₂O₃. Apart from 1,4-naphthoquinone, which is the main intermediate product in all cases, 2-naphthol, phthalide, phthaldialdehyde, phthalic acid, acetophenone, benzaldehyde, benzoic acid are also formed on dry TiO₂. Depending on their volatility, these compounds are transferred to the gas phase or remain principally adsorbed on the solid particles where they are further transformed. For instance, phthalic acid (or anhydride) and benzoic acid are generated from 1,4-naphthoquinone. Degradation mechanisms are briefly discussed.     

Potential consequences of projected climate change impacts on hydroelectricity generation

There is a growing concern that countries should reduce their dependence on fossil fuels for electricity generation and look to other cleaner technologies. Hydroelectricity is one such option. However, given that hydropower is dependent on rainfall and associated runoff for power generation, it is susceptible to both the positive and negative impacts of climate change, such as increases in temperature and changes in precipitation and runoff. In this paper, impacts on hydropower generation have been organised as either changes in long-term trends or short-term variability and shocks. These impacts could either manifest themselves as direct impacts on hydropower generation potential or as indirect impacts (or ancillary impacts) such as increased competition for water. Citing examples from around the world, this paper investigates the scale of these projected impacts, and the potential cost implication of inaction. It concludes by making recommendations for possible adaptive options to build resilience in response to local impacts.     

The LMDZ4 general circulation model: climate performance and sensitivity to parametrized physics with emphasis on tropical convection

The LMDZ4 general circulation model is the atmospheric component of the IPSL–CM4 coupled model which has been used to perform climate change simulations for the 4th IPCC assessment report. The main aspects of the model climatology (forced by observed sea surface temperature) are documented here, as well as the major improvements with respect to the previous versions, which mainly come form the parametrization of tropical convection. A methodology is proposed to help analyse the sensitivity of the tropical Hadley–Walker circulation to the parametrization of cumulus convection and clouds. The tropical circulation is characterized using scalar potentials associated with the horizontal wind and horizontal transport of geopotential (the Laplacian of which is proportional to the total vertical momentum in the atmospheric column). The effect of parametrized physics is analysed in a regime sorted framework using the vertical velocity at 500 hPa as a proxy for large scale vertical motion. Compared to Tiedtke’s convection scheme, used in previous versions, the Emanuel’s scheme improves the representation of the Hadley–Walker circulation, with a relatively stronger and deeper large scale vertical ascent over tropical continents, and suppresses the marked patterns of concentrated rainfall over oceans. Thanks to the regime sorted analyses, these differences are attributed to intrinsic differences in the vertical distribution of convective heating, and to the lack of self-inhibition by precipitating downdraughts in Tiedtke’s parametrization. Both the convection and cloud schemes are shown to control the relative importance of large scale convection over land and ocean, an important point for the behaviour of the coupled model.     

Evolution of the fogwater composition in Strasbourg (France) from 1990 to 1999

The chemical composition of fogwater has been studied in the city of Strasbourg (France) from 1990 to 1999. During these years, fogwater samples have been collected and analysed for major ions and trace metals. This paper reports on the analysis of the collected dataset. The analysis revealed a significant decrease in acidity of approximately one pH unit over the course of the study. This decrease in acidity appears to be linked to a decrease in SO_2(g) and the resulting SO₄²⁻. Trace metal concentrations have also strongly decreased over the 10-year period. Pb concentrations, following the elimination of leaded gasoline, decreased by more than one order of magnitude.