Analysis of Sediments and Soils by X-Ray Fluorescence Spectrometry Using Matrix Corrections Based on Fundamental Parameters

Wavelength dispersive X-ray fluorescence spectrometry (WD-XRF) is widely used for the analysis of soils and sediments using well characterised procedures. However, difficulties can occur with samples such as unknowns containing small amounts of ore materials and samples collected from contaminated sites where trace elemental concentrations can exceed the concentration range for routine analysis. We studied the performance of a commercially available method, based on fundamental parameters (FP) to correct matrix effects. The spectrometer was originally calibrated with elemental or simple compound calibrants. Samples were analysed as pressed powder pellets. Eighteen sediment and soil reference materials, three of them with certified values for some of their constituents, were used to evaluate accuracy, by comparing results with recommended values and their standard deviations (RV ± 2s) or certified values and their confidence intervals (CV ± Cl). When results fell systematically outside these intervals, calibrations were refined with geochemical reference materials. The best agreement of results with recommended and certified values was obtained when the contents of H₂O and C in each sample were included as matrix constituents during calculations. The detection limits of trace elements tended to be relatively high, because the measuring conditions employed were not maximised for sensitivity. The main advantage of the method tested was that it enabled the analysis of samples with high concentrations of trace elements and the determination of elements such as F, Bi, Sb and W, which are not commonly included in quantitative XRF analysis of geological samples.     

A mass transfer model of bauxite formation

The formation of bauxite due to weathering of a granitic protolith has been simulated by means of a one-dimensional flow and reaction model based on the mass transfer principle. The model couples mineral dissolution and precipitation reactions, speciation in solution, and advective solute transport in a porous medium. A very important aspect of the modeling study is the use of mineral reaction rates determined experimentally in the laboratory. The important effects of solution saturation state and pH have been incorporated into the kinetic rate laws governing the heterogeneous reactions. The values of these parameters have been obtained from the scientific literature to guarantee that realistic reaction rates are used in the simulations. Albite and quartz are the minerals that make up the parent rock in the model. Gibbsite, kaolinite, and a Na-mica (as a surrogate for smectite) are the secondary minerals that have been taken into account. Long-term simulations (>1 Ma) have been run, and the formation of a bauxitic profile, with an upper gibbsite-rich and a lower kaolinite-rich zone, is predicted. In early stages of the process (up to a few hundreds of thousands of years), both gibbsite and kaolinite precipitate directly from solution as a consequence of albite dissolution. In later stages, the bulk of gibbsite precipitation derives from the incongruent dissolution of kaolinite, while kaolinite precipitation is still caused by the dissolution of albite. This is also reflected by the formation of two reaction fronts in the profile. These results are compared with weathering sequences from the Los Pijiguaos bauxite deposit, Venezuela. The overlap between the gibbsite and kaolinite zones and the replacement of kaolinite by gibbsite are consistent with model calculations. Mechanical denudation has to be called upon to explain the limited thicknesses of the weathering profiles in the field. The role of mechanical erosion is supported by the presence of microsedimentary structures in the bauxite and the balance between dissolved and suspended loads in the streams draining the area.     

A comparative study of the modelling of cement hydration and cement-rock laboratory experiments

The use of cement and concrete as fracture grouting or as tunnel seals in a geological disposal facility for radioactive wastes creates potential issues concerning chemical reactivity. From a long-term safety perspective, it is desirable to be able model these interactions and changes quantitatively. The ‘Long-term Cement Studies’ (LCS) project was formulated with an emphasis on in situ field experiments with more realistic boundary conditions and longer time scales compared with former experiments. As part of the project programme, a modelling inter-comparison has been conducted, involving the modelling of two experiments describing cement hydration on one hand and cement-rock reaction on the other, with teams representing the NDA (UK), Posiva (Finland), and JAEA (Japan).This modelling exercise showed that the dominant reaction pathways in the two experiments are fairly well understood and are consistent between the different modelling teams, although significant differences existed amongst the precise parameterisation (e.g. reactive surface areas, dependences of rate upon pH, types of secondary minerals), and in some instances, processes (e.g. partition of alkali elements between solids and liquid during cement hydration; kinetic models of cement hydration). It was not conclusive if certain processes such as surface complexation (preferred by some modellers, but not by others) played a role in the cement-rock experiment or not. These processes appear to be more relevant at early times in the experiment and the evolution at longer timescales was not affected. The observed permeability profile with time could not be matched. The fact that no secondary minerals could be observed and that the precipitated mass calculated during the simulations is minor might suggest that the permeability reduction does not have a chemical origin, although a small amount of precipitates at pore throats could have a large impact on permeability.The modelling exercises showed that there is an interest in keeping the numerical models as simple as possible and trying to obtain a reasonable fit with a minimum of processes, minerals and parameters. However, up-scaling processes and model parameterisation to the timescales appropriate to repository safety assessment are of considerable concern. Future modelling exercises of this type should focus on a suitable natural or industrial analogue that might aid assessing mineral-fluid reactions at these longer timescales.     

An Intercomparison of Large-Eddy Simulations of the Stable Boundary Layer

Results are presented from the first intercomparison of large-eddy simulation (LES) models for the stable boundary layer (SBL), as part of the Global Energy and Water Cycle Experiment Atmospheric Boundary Layer Study initiative. A moderately stable case is used, based on Arctic observations. All models produce successful simulations, in as much as they generate resolved turbulence and reflect many of the results from local scaling theory and observations. Simulations performed at 1-m and 2-m resolution show only small changes in the mean profiles compared to coarser resolutions. Also, sensitivity to subgrid models for individual models highlights their importance in SBL simulation at moderate resolution (6.25 m). Stability functions are derived from the LES using typical mixing lengths used in numerical weather prediction (NWP) and climate models. The functions have smaller values than those used in NWP. There is also support for the use of K-profile similarity in parametrizations. Thus, the results provide improved understanding and motivate future developments of the parametrization of the SBL.     

Future regional projections of extreme temperatures in Europe: a nonstationary seasonal approach

This paper analyzes changes of maximum temperatures in Europe, which are evaluated using two state-of-the-art regional climate models from the EU ENSEMBLES project. Extremes are expressed in terms of return values using a time-dependent generalized extreme value (GEV) model fitted to monthly maxima. Unlike the standard GEV method, this approach allows analyzing return periods at different time scales (monthly, seasonal, annual, etc). The study focuses on the end of the 20th century (1961?C2000), used as a calibration/validation period, and assesses the changes projected for the period 2061?C2100 considering the A1B emission scenario. The performance of the regional models is evaluated for each season of the calibration period against the high-resolution gridded E-OBS dataset, showing a similar South-North gradient with larger values over the Mediterranean basin. The inter-RCM changes in the bias pattern with respect to the E-OBS are larger than the bias resulting from a change in the boundary conditions from ERA-40 to ECHAM5 20c3m. The maximum temperature response to increased green house gases, as projected by the A1B scenario, is consistent for both RCMs. Under that scenario, results indicate that the increments for extremes (e.g. 40-year return values) will be two or three times higher than those for the mean seasonal temperatures, particularly during Spring and Summer in Southern Europe.     

Study of an unexpected convective storm

The occurrence of a severe storm in the Argentine littoral has been analyzed. Although general atmospheric conditions were not favorable to the development of deep convection, this storm produced strong winds and hail of considerable intensity. Its occurrence was associated with the entrance of a pulse of humid air at low levels and could be related to the development of two vorticity centers in the region. Atmospheric conditions existing above a low-level inversion are used to simulate two possible clouds, with base altitudes at 2200 and 3000 m and updraft speeds reaching maximum values of 27 and 29 m s⁻¹ respectively. It is noted that the base temperature of about 13°C, found for the first cloud, can be correlated with the prevalence of frozen drop embryos, observed in an analyzed hailstone sample. Hailstone vertical trajectories are simulated in both modeled clouds, assuming spheroidal and spherical particles and assigning different values to the drag coefficient C_d.     

Impact of anthropogenic CO 2 on the next glacial cycle

The model of Paillard and Parrenin (Earth Planet Sci Lett 227(3–4):263–271, 2004) has been recently optimized for the last eight glacial cycles, leading to two different relaxation models with model-data correlations between 0.8 and 0.9 (García-Olivares and Herrero (Clim Dyn 1–25, 2012b)). These two models are here used to predict the effect of an anthropogenic CO ₂ pulse on the evolution of atmospheric CO ₂, global ice volume and Antarctic ice cover during the next 300 kyr. The initial atmospheric CO ₂ condition is obtained after a critical data analysis that sets 1300 Gt as the most realistic carbon Ultimate Recoverable Resources (URR), with the help of a global compartmental model to determine the carbon transfer function to the atmosphere. The next 20 kyr will have an abnormally high greenhouse effect which, according to the CO ₂ values, will lengthen the present interglacial by some 25 to 33 kyr. This is because the perturbation of the current interglacial will lead to a delay in the future advance of the ice sheet on the Antarctic shelf, causing that the relative maximum of boreal insolation found 65 kyr after present (AP) will not affect the developing glaciation. Instead, it will be the following insolation peak, about 110 kyr AP, which will find an appropriate climatic state to trigger the next deglaciation.     

气象卫星云图的多分辨小波分解及人工神经网络降水估计研究

采用多分辨小波分析对卫星图象进行预处理 ,在保留其特征信息的同时 ,减小了数据量 ,改善了神经网络训练过程的收敛性能 ,提高了处理速度。采用这一方法根据 GOES- 8的红外亮温图象和气象雷达资料对巴西圣保罗州中部的降水量估计进行了试验 ,取得了良好的效果。