A Compilation of Silicon,Rare Earth Element and Twenty‐One other Trace Element Concentrations in the Natural River Water Reference Material SLRS‐5 (NRC‐CNRC)

The natural river water certified reference material SLRS‐5 (NRC‐CNRC) was routinely analysed in this study for major and trace elements by ten French laboratories. Most of the measurements were made using ICP‐MS. Because no certified values are assigned by NRC‐CNRC for silicon and 35 trace element concentrations (rare earth elements, Ag, B, Bi, Cs, Ga, Ge, Li, Nb, P, Rb, Rh, Re, S, Sc, Sn, Th, Ti, Tl, W, Y and Zr), or for isotopic ratios, we provide a compilation of the concentrations and related uncertainties obtained by the participating laboratories. Strontium isotopic ratios are also given.     

Proximal and distal styles of pegmatite-related metasomatic emerald mineralization at Ianapera,southern Madagascar

The Ianapera emerald deposit is located in the Neoproterozoic Vohibory Block of southern Madagascar. The local geology consists of intercalated migmatitic gneissic units and calcareous metasedimentary rocks, containing boudinaged metamorphosed mafic/ultramafic lenses, all intruded by pegmatite veins. These units occur near the hinge of the tightly folded Ianapera antiform, within a few kilometers of the Ampanihy shear zone. Emerald mineralization is hosted by metasomatic phlogopite veins, and bodies developed within the mafic/ultramafic rocks. Based on field and textural relationships, we distinguish proximal and distal styles of mineralization. Proximal mineralization occurs at the contact of pegmatite veins with mafic/ultramafic units; in the distal style, pegmatites are not observed. Three types of emeralds could be distinguished, mainly on the basis of color and mineral zoning. Some of these emeralds have the most Al-depleted and Cr-rich composition ever recorded. Another characteristic feature to the Ianapera deposit and, to our knowledge, yet unreported, is the association of some emeralds with scapolite in metasomatised mafic rocks. Mineral inclusions are common in most emeralds and include phlogopite, carbonates, barite, K-feldspar, quartz, pyrite, zircon, monazite, bastnaesite, phenakite, plus Fe and Cr oxides. However, feldspar and rare earth element-bearing minerals occur predominantly in proximal emeralds, which also have a more incompatible trace-element signature than distal emeralds. We propose a model related to syn- to post-tectonic magmatic-hydrothermal activity. Pegmatitic bodies intruded units of the Ianapera antiform probably during tectonic relaxation. Exsolution of fluids rich in halogens and incompatible elements from the cooling pegmatites caused hydrothermal metasomatism of Cr-bearing mafic/ultramafic rocks in direct contact with the pegmatites. Local fracturing favored fluid infiltration, permitting the formation of distal mineralization. Emerald composition was controlled by the chemistry of the host rock. The presence of carbonate mineral inclusions in the emeralds and the high F-activity indicated by elevated F-contents in newly formed minerals suggest transport of Be as a fluoride-carbonate complex. It seems likely that beryl formation was triggered by precipitation of F-rich phlogopite, which removed the complexing ligand from the fluid.     

The Removal of Dissolved Metals by Hydroxysulphate Precipitates during Oxidation and Neutralization of Acid Mine Waters, Iberian Pyrite Belt

This study examines the removal of dissolved metals during the oxidation and neutralization of five acid mine drainage (AMD) waters from La Zarza, Lomero, Esperanza, Corta Atalaya and Poderosa mines (Iberian Pyrite Belt, Huelva, Spain). These waters were selected to cover the spectrum of pH (2.2–3.5) and chemical composition (e.g., 319–2,103 mg/L Fe; 2.85–33.3 g/L SO₄⁼) of the IPB mine waters. The experiments were conducted in the laboratory to simulate the geochemical evolution previously recognized in the field. This evolution includes two stages: (1) oxidation of dissolved Fe(II) followed by hydrolysis and precipitation of Fe(III), and (2) progressive pH increase during mixing with fresh waters. Fe(III) precipitates at pH < 3.5 (stages 1 and 2) in the form of schwertmannite, whereas Al precipitates during stage 2 at pH 5.0 in the form of several hydroxysulphates of variable composition (hydrobasaluminite, basaluminite, aluminite). During these stages, trace elements are totally or partially sorbed and/or coprecipitated at different rates depending basically on pH, as well as on the activity of the SO₄⁼ anion (which determines the speciation of metals). The general trend for the metals which are chiefly present as aqueous free cations (Pb²⁺, Zn²⁺, Cu²⁺, Cd²⁺, Mn²⁺, Co²⁺, Ni²⁺) is a progressive sorption at increasing pH. On the other hand, As and V (mainly present as anionic species) are completely scavenged during the oxidation stage at pH < 3.5. In waters with high activities (> 10⁻¹) of the SO ₄⁼ ion, some elements like Al, Zn, Cd, Pb and U can also form anionic bisulphate complexes and be significantly sorbed at pH < 5. The removal rates at pH 7.0 range from around 100% for As, V, Cu and U, and 60–80% for Pb, to less than 20% for Zn, Co, Ni and Mn. These processes of metal removal represent a significant mechanism of natural attenuation in the IPB.     

A Monte Carlo Model Of The Nocturnal Surface Temperatures In Urban Canyons

A model for the urban canyon is formulated for meteorologicalconditions of weak winds at night time. Thermal radiation, conductivity and convection are simulated by means of the Monte Carlo method. These are the main physical processesof energy transfer that give rise to the characteristic temperaturedistribution in these systems. The model has been satisfactory tested under ideal conditions for which analytical solutions exist.The predictions of the model under morerealistic conditions accurately reproduce the observationalresults. A strong temperature gradient across streets, with the canyon corners up to 4 °C warmer than the canyon centre, is found for the deepest canyons. This theoretical predictionhas been successfully verified with measurementstaken in a number of streets of the city of Granada in Spain.     

Anthropogenic climate change over the Mediterranean region simulated by a global variable resolution model

Two 30-year simulations corresponding to 1960-1989 and 2070-2099 have been performed with a variable resolution atmospheric model. The model has a maximum horizontal resolution of 0.5° over the Mediterranean Sea. Simulations are driven by IPCC-B2 scenario radiative forcing. Sea surface temperatures (SSTs) are prescribed from monthly observations for the present climate simulation, and from a blend of observations and coupled simulations for the scenario. Another pair of forced atmospheric simulations has been run under these forcings with the same uniform low resolution as the coupled model. Comparisons with observations show that the variable resolution model realistically reproduces the main climate characteristics of the Mediterranean region. At a global scale, changes in latitudinal temperature profiles are similar for the forced and coupled models, justifying the time-slice approach. The 2 m temperature and precipitation responses predict a warming and drying of the Mediterranean region. A comparison with the coupled simulation and forced low-resolution simulation shows that this pattern is robust. The decrease in mean precipitation is associated with a significant decrease in soil wetness, and could involve considerable impact on water resources around the Mediterranean basin.     

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.     

A Simple And General Subgrid Model Suitable Both For Surface Layer And Free-Stream Turbulence

A new and general approach is presented to allow standard subgrid schemes to besuitable both for surface layer and free-stream turbulence. Simple modificationsto subgrid schemes are proposed and derived for any vertical stabilityconditions. They are simple to implement in models and are suitable for morecomplicated simulations such as large-eddy simulation with inhomogeneoussurface conditions or complex topography. They are also applicable to mesoscaleand large-scale models. These modifications are physically justified by recentmeasurements of spectra close to the ground. The spectral analysis presentedshows how the energy deficit of blocked turbulence for a given dissipation(`anomalous dissipation') dramatically affects the coefficients to be used insubgrid schemes. As shown for neutral and convective cases with wind shear,these changes allow us to substantially improve the prediction of profiles for themean quantities in the surface layer. Agreement with similarity laws in the unstablecase is found up to about 0.2z_i, for simulated shear, stabilityprofiles and dissipation rates of turbulent kinetic energy.     

Evaluation of a high-resolution regional climate simulation over Greenland

A simulation of the 1991 summer has been performed over south Greenland with a coupled atmosphere–snow regional climate model (RCM) forced by the ECMWF re-analysis. The simulation is evaluated with in-situ coastal and ice-sheet atmospheric and glaciological observations. Modelled air temperature, specific humidity, wind speed and radiative fluxes are in good agreement with the available observations, although uncertainties in the radiative transfer scheme need further investigation to improve the model’s performance. In the sub-surface snow-ice model, surface albedo is calculated from the simulated snow grain shape and size, snow depth, meltwater accumulation, cloudiness and ice albedo. The use of snow metamorphism processes allows a realistic modelling of the temporal variations in the surface albedo during both melting periods and accumulation events. Concerning the surface albedo, the main finding is that an accurate albedo simulation during the melting season strongly depends on a proper initialization of the surface conditions which mainly result from winter accumulation processes. Furthermore, in a sensitivity experiment with a constant 0.8 albedo over the whole ice sheet, the average amount of melt decreased by more than 60%, which highlights the importance of a correctly simulated surface albedo. The use of this coupled atmosphere–snow RCM offers new perspectives in the study of the Greenland surface mass balance due to the represented feedback between the surface climate and the surface albedo, which is the most sensitive parameter in energy-balance-based ablation calculations.     

Magmatic-to-hydrothermal crystallization in the W–Sn mineralized Mole Granite (NSW, Australia): Part I: Crystallization of zircon and REE-phosphates over three million years—a geochemical and U–Pb geochronological study

Zircon, monazite and xenotime crystallized over a temperature interval of several hundred degrees at the magmatic to hydrothermal transition of the Sn and W mineralized Mole Granite. Magmatic zircon and monazite, thought to have crystallized from hydrous silicate melt, were dated by conventional U–Pb techniques at an age of 247.6 ± 0.4 and 247.7 ± 0.5 Ma, respectively. Xenotime occurring in hydrothermal quartz is found to be significantly younger at 246.2 ± 0.5 Ma and is interpreted to represent hydrothermal growth. From associated fluid inclusions it is concluded that it precipitated from a hydrothermal brine ≤ 600 °C, which is below the accepted closure temperature for U–Pb in this mineral. These data are compatible with a two-stage crystallization process: precipitation of zircon and monazite as magmatic liquidus phases in deep crustal magma followed by complete crystallization and intimately associated Sn–W mineralization after intrusion of the shallow, sill-like body of the Mole Granite. Later hydrothermal formation of monazite in a biotite–fluorite–topaz reaction rim around a mineralized vein was dated at 244.4 ± 1.4 Ma, which distinctly postdates the Mole Granite and is possibly related to a younger hidden intrusion and its hydrothermal fluid system.

Obtaining precise age data for magmatic and hydrothermal minerals of the Mole Granite is hampered by uncertainties introduced by different corrections required for multiple highly radiogenic minerals crystallising from evolved hydrous granites, including ²³⁰Th disequilibrium due to Th/U fractionation during monazite and possibly xenotime crystallization, variable Th/U ratios of the fluids from which xenotime was precipitating, elevated contents of common lead, and post-crystallization lead loss in zircon, enhanced by the fluid-saturated environment. The data imply that monazite can also survive as a liquidus phase in protracted magmatic systems over periods of 10⁶ years. The outlined model is in agreement with prominent chemical core-rim variation of the zircon.     

Dissolution of calcitic marble and dolomitic rock in high iron concentrated acid mine drainage: application to anoxic limestone drains

Oxidation of sulphide mining waste can generate acid mine drainage (AMD) that has the potential to seriously affect the ecosystems. Acid mine drainage is characterised by a high acidity, high concentrations of sulphates and metals. To reduce the environmental impacts due to AMD, neutralisation using limestone drains is an option proposed in the literature and used around the world. The present study focuses on the influence of the carbonate rock mineralogy and their particle size on the neutralising capacity. The tests were performed in two different anoxic conditions: in batch reactors, and in columns having a hydraulic retention time of 15?h. The results showed that the neutralisation capacity of calcite was more important than for dolomitic rock, and smaller particle size gave higher alkalinity production (fine calcite dissolved faster in contact with AMD). A characterization of metal precipitate in sludge and in limestone coating was performed and demonstrated that gypsum, lepidocrocite and goethite were the predominant secondary minerals to be formed. Finally, this study underlines that anoxic limestone drain cannot be used alone to treat high iron concentrated AMD.