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 CrO42? 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. 相似文献
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. 相似文献
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. 相似文献
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. 相似文献
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. 相似文献
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. 相似文献
General circulation model outputs are rarely used directly for quantifying climate change impacts on hydrology, due to their coarse resolution and inherent bias. Bias correction methods are usually applied to correct the statistical deviations of climate model outputs from the observed data. However, the use of bias correction methods for impact studies is often disputable, due to the lack of physical basis and the bias nonstationarity of climate model outputs. With the improvement in model resolution and reliability, it is now possible to investigate the direct use of regional climate model (RCM) outputs for impact studies. This study proposes an approach to use RCM simulations directly for quantifying the hydrological impacts of climate change over North America. With this method, a hydrological model (HSAMI) is specifically calibrated using the RCM simulations at the recent past period. The change in hydrological regimes for a future period (2041–2065) over the reference (1971–1995), simulated using bias‐corrected and nonbias‐corrected simulations, is compared using mean flow, spring high flow, and summer–autumn low flow as indicators. Three RCMs driven by three different general circulation models are used to investigate the uncertainty of hydrological simulations associated with the choice of a bias‐corrected or nonbias‐corrected RCM simulation. The results indicate that the uncertainty envelope is generally watershed and indicator dependent. It is difficult to draw a firm conclusion about whether one method is better than the other. In other words, the bias correction method could bring further uncertainty to future hydrological simulations, in addition to uncertainty related to the choice of a bias correction method. This implies that the nonbias‐corrected results should be provided to end users along with the bias‐corrected ones, along with a detailed explanation of the bias correction procedure. This information would be especially helpful to assist end users in making the most informed decisions. 相似文献
Historically, paired watershed studies have been used to quantify the hydrological effects of land use and management practices by concurrently monitoring 2 similar watersheds during calibration (pretreatment) and post‐treatment periods. This study characterizes seasonal water table and flow response to rainfall during the calibration period and tests a change detection technique of moving sums of recursive residuals (MOSUM) to select calibration periods for each control–treatment watershed pair when the regression coefficients for daily water table elevation were most stable to minimize regression model uncertainty. The control and treatment watersheds were 1 watershed of 3–4‐year‐old intensely managed loblolly pine (Pinus taeda L.) with natural understory, 1 watershed of 3–4‐year‐old loblolly pine intercropped with switchgrass (Panicum virgatum), 1 watershed of 14–15‐year‐old thinned loblolly pine with natural understory (control), and 1 watershed of switchgrass only. The study period spanned from 2009 to 2012. Silvicultural operational practices during this period acted as external factors, potentially shifting hydrologic calibration relationships between control and treatment watersheds. MOSUM results indicated significant changes in regression parameters due to silvicultural operations and were used to identify stable relationships for water table elevation. None of the calibration relationships developed using this method were significantly different from the classical calibration relationship based on published historical data. We attribute that to the similarity of historical and 2010–2012 leaf area index on control and treatment watersheds as moderated by the emergent vegetation. Although the MOSUM approach does not eliminate the need for true calibration data or replace the classic paired watershed approach, our results show that it may be an effective alternative approach when true data are unavailable, as it minimizes the impacts of external disturbances other than the treatment of interest. 相似文献