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.     

Environmental records of carbonaceous fly-ash particles from fossil-fuel combustion

Analysis of fly-ash particles in lake sediments has become increasingly important in studies of environmental pollution and lake acidification history. Most fly-ash studies have concerned black spheroidal carbonaceous particles (SCP)(>5 m) produced from oil and coal combustion. This review paper provides a summary of this technique and its application, and focusses on our investigations in Sweden between 1979 and 1993. It consists of five parts: i) preparation and analysis methods, ii) historical trends in atmospheric deposition, iii) geographical surveys of atmospheric deposition, iv) sediment dating, and v) studies of sedimentation processes in lakes. Methods for preparation and analyses of SCP have been developed and applied to investigations using sediment, soil and snow samples. Stratigraphic trends of SCP concentrations in lake-sediment cores reflect the consumption history of fossil fuels. A characteristic temporal SCP pattern, with a marked concentration increase beginning after the 1940's and a peak in the early 1970's, has been recognized in most Swedish lakes and elsewhere in Europe. A survey of SCP concentrations in surface sediments of >100 lakes covering Sweden demonstrated that polluted areas in southern Sweden had >100 times higher SCP concentrations than clean areas in the north. The spatial distribution of SCP over Sweden is similar to the deposition pattern of long-range transported airborne pollutants, such as excess sulphate monitored by network stations. SCP also accumulate in soils, and soil analyses can be used for determining the integrated historical deposition of SCP at the local or regional scale. Finally, SCP have been used for indirect dating of sediment cores and as a marker to assess sediment distribution patterns within lake basins.     

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.     

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。     

The Role of Planetary Boundary-Layer Parameterizations in the Air Quality of an Urban Area with Complex Topography

The effect of different planetary boundary-layer (PBL) parameterization schemes on the spatial distribution of atmospheric pollution over the complex topography of the greater Athens area is investigated. Four PBL schemes originally implemented in a numerical meteorological model and a fifth one simulating the urban effect are examined. Two different atmospheric conditions are analyzed; a typical summer and a typical winter pollution episode. The relative importance of chemical and physical processes of the pollution predictions is discussed using process analysis. It is revealed that, for primary pollutants, a local scheme seems more adequate to represent the maximum observed concentrations while, completely different in structure, a non-local scheme reproduces the mean observed values in the basin. Concerning secondary pollutants, peak concentration differences, due to the different PBL schemes, are smoothed out. Nevertheless, the PBL scheme selection shapes the horizontal and the vertical extension of maximum values. The non-local and semi non-local schemes are superior to the others, favouring strong vertical mixing and transport towards the surface. The stronger turbulence accommodated effectively by the semi non-local urban scheme enhances ozone production along the sea-breeze axis and preserves the high ozone concentrations during the nighttime hours in the urban core.