Environmental controls on clay mineralogy of an Early Jurassic mudrock (Blue Lias Formation,southern England)

We present a dataset including clay mineralogy, gamma-ray spectrometry, organic matter content and magnetic susceptibility of the Hettangian to lowest Sinemurian successions of Dorset and Somerset, southern UK (Blue Lias Formation, Bristol Channel and Wessex basins). In both areas, the clay assemblages comprise predominantly detrital illite, kaolinite and illite/smectite mixed layers. Clays probably originated from the erosion of the Hercynian massifs, the relative proportions of kaolinite and illite being modulated by arid-humid climatic fluctuations. The organic matter (OM) content (types II to IV) ranges up to 12% in both areas. A clear stratigraphical trend in clay mineral assemblages is apparent in Somerset, whereas in Dorset sharp contrasts between adjacent horizons and a greater dilution by carbonate mask the long-term evolution. Correlations between both areas based on similar vertical trends in clay mineral abundance support the suggestion of a hiatus within the angulata Zone of the Dorset succession. As expected, the kaolinite/illite ratio correlates with the Th/K ratio deduced from gamma-ray spectrometry. However, significant departures from the correlation occur in OM-rich intervals, suggesting that Th may be partly adsorbed on to OM particles. Surprisingly, high magnetic susceptibility correlates with abundant kaolinite, not with Fe-rich clays, indicating either that kaolinite is accompanied by a soil-inherited magnetisable phase (possibly iron oxide) or that illite-rich rocks are more strongly diluted by carbonate than are kaolinite-rich strata.     

Chromium speciation in oxide-type compounds: application to minerals,gems, aqueous solutions and silicate glasses

Cr K-edge XANES spectra were obtained for a variety of Cr-bearing model compounds containing Cr(II), Cr(III), Cr(IV), Cr(V) and Cr(VI), in which the Cr-site symmetry is D4h, Oh and Td. The centroid position of the pre-edge feature is a better indicator of the Cr valence than the edge position. In Cr-rich oxides, higher-energy transitions must be excluded in order to refine a robust valence for Cr. The pre-edge for chromates is not unique and varies as a function of the CrO₄ ^2? moiety distortion, which is often related to Cr-polymerization (monochromate vs. dichromate). Both the analogy with the Mn K-pre-edge information and ab initio FEFF calculations of the pre-edge feature for Cr(III) and Cr(VI) confirm the experimental trends. This methodology is applied to the Cr K-edge pre-edge feature collected in gems (emerald, spinel and ruby), the layered minerals fuchsite and kämmererite, two Cr-bearing aqueous solutions and a set of sodo-calcic silicate glasses used for bottling sparkling white wine. In emerald and fuchsite, the Cr-site is differently distorted than its ruby or spinel counterpart. In a Cr(III)-bearing aqueous solution and sodo-calcic glass, no evidence for Cr(III) with Td and C3v symmetry is detected. However, minor amounts of chromate moieties (most likely monomeric) are detected in a glass synthesized in air. Preliminary spectra for the wine bottle glass suggest that only trace amounts of chromates might possibly be present in these glasses.     

Quaternary geochemical evolution of the salars of Uyuni and Coipasa, Central Altiplano, Bolivia

The central trough of the Bolivian Altiplano is occupied by two wide salt crusts: the salar of Uyuni, which is probably the largest salt pan in the world (10,000 km²) and the salar of Coipasa (2,500 km²). Both crusts are essentially made of porous halite filled with an interstitial brine very rich in Li, K, Mg, B (up to 4.7 g/l Li, 4.3 g/l B, 30 g/l K and 75 g/l Mg). Lithium reserves are the highest known in the world, around 9 × 10⁶ tons. Potassium, magnesium and boron reserves in brines are also important (around 194 × 10⁶ tons K, 8 × 10⁶ tons B and 211 × 10⁶ tons Mg).

The crusts are the remnant of saline Lake Tauca (13,000–10,000 yr BP). Its salinity was estimated approximately at 80 g/l. Its paleochemistry was derived in two ways: (1) by dissolving the present amounts of all chemical components in the former lake volume, and (2) by simulating the evaporation of the major inflows to the basin. The resulting chemical compositions are quite different. The dissolution-derived one is 5 to 50 times less concentrated in Li, K, Mg, B than the evaporation-simulated ones. However all compositions present the same Na and Cl contents. This suggests either a removal of bittern salts or an enrichment of the former lake water in Na and Cl.

The most probable interpretation is that Lake Tauca redissolved a salt crust akin to that existing today. Several older lakes have been detected on the Altiplano. Nevertheless, such an explanation only pushes the problem back. It is likely that the anomaly was transferred from one lake to an other. Three hypotheses may be put forward: (1) bittern seepage through bottom sediments, (2) uptake of the missing components by minerals, and (3) leaching of ancient evaporites from the catchment area at the beginning of the lacustrine history of the basin. The excess halite could have been recycled from lake to lake. This latter process seems to be the most effective to explain the large excess of Na and Cl over the bittern solutes — Li, K, Mg and B. The occurrence of almost pure Na/1bCl saline springs flowing out from a gypsum diapir in the northern Altiplano gives substantial support to this hypothesis.     

Occurence of abundant diradicaloid moieties in the insoluble organic matter from the Orgueil and Murchison meteorites: a fingerprint of its extraterrestrial origin?

The highly aromatic structure of the macromolecular organic matter (OM) of the Murchison and Orgueil meteorites was recently shown to contain free organic radicals which are concentrated in micro-regions in contrast with terrestrial samples which always show an homogeneous distribution of radicals. An additional signature is revealed, in the present study, by the evolution of the radical concentration with temperature. Whereas in terrestrial samples, this concentration is independent of temperature (Curie magnetism), a significant increase is observed above 150 K in the two meteorites. Based on the electronic structure of organic radicals, calculated by Extended Hückel and Density Functional methods, this behavior was assigned to the occurrence of diradicaloid moieties hosted by aromatic structures of 10 to 15 rings and having a quinoidal structure. They represent 40 and 25% of the total radicals in Orgueil and Murchison, respectively. The search for the cosmochemical interpretation of this unique observation should open a new field of experimental investigations.     

Coupling statistical and dynamical methods for spatial downscaling of precipitation

The resolution of General Circulation Models (GCMs) is too coarse for climate change impact studies at the catchment or site-specific scales. To overcome this problem, both dynamical and statistical downscaling methods have been developed. Each downscaling method has its advantages and drawbacks, which have been described in great detail in the literature. This paper evaluates the improvement in statistical downscaling (SD) predictive power when using predictors from a Regional Climate Model (RCM) over a GCM for downscaling site-specific precipitation. Our approach uses mixed downscaling, combining both dynamic and statistical methods. Precipitation, a critical element of hydrology studies that is also much more difficult to downscale than temperature, is the only variable evaluated in this study. The SD method selected here uses a stepwise linear regression approach for precipitation quantity and occurrence (similar to the well-known Statistical Downscaling Model (SDSM) and called SDSM-like herein). In addition, a discriminant analysis (DA) was tested to generate precipitation occurrence, and a weather typing approach was used to derive statistical relationships based on weather types, and not only on a seasonal basis as is usually done. The existing data record was separated into a calibration and validation periods. To compare the relative efficiency of the SD approaches, relationships were derived at the same sites using the same predictors at a 300km scale (the National Center for Environmental Prediction (NCEP) reanalysis) and at a 45km scale with data from the limited-area Canadian Regional Climate Model (CRCM) driven by NCEP data at its boundaries. Predictably, using CRCM variables as predictors rather than NCEP data resulted in a much-improved explained variance for precipitation, although it was always less than 50?% overall. For precipitation occurrence, the SDSM-like model slightly overestimated the frequencies of wet and dry periods, while these were well-replicated by the DA-based model. Both the SDSM-like and DA-based models reproduced the percentage of wet days, but the wet and dry statuses for each day were poorly downscaled by both approaches. Overall, precipitation occurrence downscaled by the DA-based model was much better than that predicted by the SDSM-like model. Despite the added complexity, the weather typing approach was not better at downscaling precipitation than approaches without classification. Overall, despite significant improvements in precipitation occurrence prediction by the DA scheme, and even going to finer scales predictors, the SD approach tested here still explained less than 50?% of the total precipitation variance. While going to even smaller scale predictors (10–15?km) might improve results even more, such smaller scales would basically transform the direct outputs of climate models into impact models, thus negating the need for statistical downscaling approaches.     

Trace Metal Solid State Speciation in Aerosols of the Northern Levantine Basin,East Mediterranean

An established three stage sequential leach scheme was applied to a series of selected high volume aerosol samples (n = 35) collected from the Turkish Eastern Mediterranean coastline (Erdemli). Samples were selected according to their air mass back trajectory history to reflect the contrasting mixtures of aerosol material present in the Eastern Mediterranean marine aerosol. Two populations were adopted, those samples which were classed as “anthropogenic” and those which were “Saharan” dominated aerosol populations. Applying the three stage leach it was possible to define the proportion for each of the considered metals (Al, Fe, Cu, Pb, Cd, Zn and Mn) present in the (a) “exchangeable” (b) “carbonate / oxide” and (c) “refractory” phases, representing novel solid state aerosol speciation data for this marine system. Clear trends were established, conforming with data from previous studies with mainly crustal derived metals (Al and Fe) being present in the refractory phases (Al > 88%; Fe > 84%) and those influenced by anthropogenic sources being dominating in the exchangeable phase, although for these metals the variability was comparatively high (12–64%; 19–85%; 40–100% for Zn, Pb and Cd, respectively). For the majority, greater exchangeable fractions were present the lower the crustal source contribution to the aerosol population, whereas the “refractory” fraction exhibited contrasting behaviour. This was illustrated by the novel application of the mixing diagram, presenting each of the three speciation stages against the corresponding percent anthropogenic contribution to each collected sample. Zn, Pb and Cd all illustrated progressive decrease in the percent exchangeable with increasing crustal contribution to the aerosol population. The percent exchangeable was discussed in terms of its use to represent the upper limit of the bioavailable fraction of metal associated with the aerosol, post deposition. The mixing diagram approach enabled the prediction of the residual fractions for Cd, Pb and Zn (41 ± 4%; 62 ± 4% and 82 ± 5%, respectively,) in Saharan end-member material.     

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.     

The stratospheric version of LMDz: dynamical climatologies, arctic oscillation, and impact on the surface climate

A climatology of the stratosphere is determined from a 20-year integration with the stratospheric version of the Atmospheric General Circulation Model LMDz. The model has an upper boundary at near 65 km, uses a Doppler spread non-orographic gravity waves drag parameterization and a subgrid-scale orography parameterization. It also has a Rayleigh damping layer for resolved waves only (not the zonal mean flow) over the top 5 km. This paper describes the basic features of the model and some aspects of its radiative-dynamical climatology. Standard first order diagnostics are presented but some emphasis is given to the model’s ability to reproduce the low frequency variability of the stratosphere in the winter northern hemisphere. In this model, the stratospheric variability is dominated at each altitudes by patterns which have some similarities with the arctic oscillation (AO). For those patterns, the signal sometimes descends from the stratosphere to the troposphere. In an experiment where the parameterized orographic gravity waves that reach the stratosphere are exaggerated, the model stratosphere in the NH presents much less variability. Although the stratospheric variability is still dominated by patterns that resemble to the AO, the downward influence of the stratosphere along these patterns is near entirely lost. In the same time, the persistence of the surface AO decreases, which is consistent with the picture that this persistence is linked to the descent of the AO signal from the stratosphere to the troposphere. A comparison between the stratospheric version of the model, and its routinely used tropospheric version is also done. It shows that the introduction of the stratosphere in a model that already has a realistic AO persistence can lead to overestimate the actual influence of the stratospheric dynamics onto the surface AO. Although this result is certainly model dependent, it suggests that the introduction of the stratosphere in a GCM also call for a new adjustment of the model parameters that affect the tropospheric variability.