Direct Current Plasma Emission Spectrometric Determination of Major, Minor and Trace Elements in Microwave Oven Acid Leachates of Powdered Whole Coal Samples

Major concentrations of Al₂O₃, Fe₂O₃, MgO, CaO, Na₂O and K₂O, minor levels of TiO₂, P₂O₅ and thirty petrologically, geochemically and environmentally significant trace elements have been determined in microwave oven acid leachates of whole powdered coal samples by direct current plasma‐atomic emission spectrometry (DCP‐AES). A single sample preparation procedure was suitable for all the determinations with no additional dilution step for major elements solution. Dried samples (0.5 g) were treated in low‐pressure PFA digestion vessels with HF/HCl/HNO₃/HClO₄ acids to quantitatively extract the analytes from the bulk material, while leaving the major part of organic matrix as a residue. The major constituents of geological samples, in particular the easily ionised elements (EIEs) such as alkali and alkaline earths, may complicate the instrumental determinations in DCP‐AES because of differential enhancements of elemental emission intensities and stray light interferences. Taking account of these factors, the coal matrix is considered to have very low major oxide totals as compared to many other common geo‐environmental and related materials (rocks, sediments, soil, ashes etc.). The sample size employed here, while yielding a relatively concentrated solution to cover a wide range of elemental determinations, provided a sample matrix that significantly diminished interferences for DCP measurements. The need for closely matching the unknowns and calibrators was eliminated except for overall acidity and an excess quantity of caesium for EIE buffering. Calibration of the spectrometer was accomplished by simple aqueous single element solutions as high concentration calibrators in addition to a reagent blank as a low concentration calibrator. Two point working curves were established to allow for the maximum concentrations of each element expected in the unknowns. The precision of determinations under routine conditions as well as the reproducibility of the leaching and precision of instrumental measurements have been evaluated. Relative standard deviations (RSD) were of 1–2% for those elements whose concentrations in solid samples were well above the limits of quantification. Method detection limits in the buffered solutions were also evaluated. To evaluate the accuracy of the microwave oven‐DCP method a suite of eight certified coal reference materials of differing rank, were analysed with good agreement with the certified and/or available published data. Results are presented for the uncertified major oxides in the AR series reference materials.     

Semi‐analytical solution to one‐dimensional consolidation for unsaturated soils with semi‐permeable drainage boundary under time‐dependent loading

This paper presents semi‐analytical solutions to Fredlund and Hasan's one‐dimensional consolidation of unsaturated soils with semi‐permeable drainage boundary under time‐dependent loadings. Two variables are introduced to transform two coupled governing equations of pore‐water and pore‐air pressures into an equivalent set of partial differential equations, which are easily solved by the Laplace transform. The pore‐water pressure, pore‐air pressure and settlement are obtained in the Laplace domain. Crump's method is adopted to perform the inverse Laplace transform in order to obtain semi‐analytical solutions in time domain. It is shown that the present solutions are more general and have a good agreement with the existing solutions from literatures. Furthermore, the current solutions can also be degenerated into conventional solutions to one‐dimensional consolidation of unsaturated soils with homogeneous boundaries. Finally, several numerical examples are provided to illustrate consolidation behavior of unsaturated soils under four types of time‐dependent loadings, including instantaneous loading, ramp loading, exponential loading and sinusoidal loading. Parametric studies are illustrated by variations of pore‐air pressure, pore‐water pressure and settlement at different values of the ratio of air–water permeability coefficient, depth and loading parameters. Copyright © 2017 John Wiley & Sons, Ltd.     

Transient seepage analysis in zoned anisotropic soils based on the scaled boundary finite‐element method

The scaled boundary finite‐element method, a semi‐analytical computational scheme primarily developed for dynamic stiffness of unbounded domains, is applied to the analysis of unsteady seepage flow problems. This method is based on the finite‐element technology and gains the advantages of the boundary element method as well. Only boundary of the domain is discretized, no fundamental solution is required and singularity problems can be modeled rigorously. Anisotropic and non‐homogeneous materials satisfying similarity are modeled with no additional efforts. In this study, firstly, formulation of the method for the transient seepage flow problems is derived followed by its solution procedures. The accuracy, simplicity and applicability of the method are demonstrated via four numerical examples of transient seepage flow – three of them are available in the literature. Homogenous, non‐homogenous, isotropic and anisotropic material properties are considered to show the versatility of the technique. Excellent agreement with the finite‐element method is observed. The method out‐performs the finite‐element method in modeling singularity points. Copyright © 2014 John Wiley & Sons, Ltd.     

Likely effects of climate change on groundwater availability in a Mediterranean region of Southeastern Spain

Groundwater resources are typically the main fresh water source in arid and semi‐arid regions. Natural recharge of aquifers is mainly based on precipitation; however, only heavy precipitation events (HPEs) are expected to produce appreciable aquifer recharge in these environments. In this work, we used daily precipitation and monthly water level time series from different locations over a Mediterranean region of Southeastern Spain to identify the critical threshold value to define HPEs that lead to appreciable aquifer recharge in this region. Wavelet and trend analyses were used to study the changes in the temporal distribution of the chosen HPEs (≥20 mm day^?1) over the observed period 1953–2012 and its projected evolution by using 18 downscaled climate projections over the projected period 2040–2099. The used precipitation time series were grouped in 10 clusters according to similarities between them assessed by using Pearson correlations. Results showed that the critical HPE threshold for the study area is 20 mm day^?1. Wavelet analysis showed that observed significant seasonal and annual peaks in global wavelet spectrum in the first sub‐period (1953–1982) are no longer significant in the second sub‐period (1983–2012) in the major part of the ten clusters. This change is because of the reduction of the mean HPEs number, which showed a negative trend over the observed period in nine clusters and was significant in five of them. However, the mean size of HPEs showed a positive trend in six clusters. A similar tendency of change is expected over the projected period. The expected reduction of the mean HPEs number is two times higher under the high climate scenario (RCP8.5) than under the moderate scenario (RCP4.5). The mean size of these events is expected to increase under the two scenarios. The groundwater availability will be affected by the reduction of HPE number which will increase the length of no aquifer recharge periods (NARP) accentuating the groundwater drought in the region. Copyright © 2016 John Wiley & Sons, Ltd.     

Measurement of stream cross section using ground penetration radar with Hilbert–Huang transform

This study presents a new method to measure stream cross section without having contact with water. Compared with conventional measurement methods which apply instruments such as sounding weight, ground penetration radar (GPR), used in this study, is a non‐contact measurement method. This non‐contact measurement method can reduce the risk to hydrologists when they are conducting measurements, particularly in high flow period. However, the original signals obtained by using GPR are very complex, different from studies in the past where the measured data were mostly interpreted by experts with special skill or knowledge of GPR so that the results obtained were less objective. This study employs Hilbert–Huang transform (HHT) to process GPR signals which are difficult to interpret by hydrologists. HHT is a newly developed signal processing method that can not only process the nonlinear and non‐stationary complex signals, but also maintain the physical significance of the signal itself. Using GPR with HHT, this study establishes a non‐contact stream cross‐section measurement method with the ability to measure stream cross‐sectional areas precisely and quickly. Also, in comparison with the conventional method, no significant difference in results is found to exist between the two methods, but the new method can considerably reduce risk, measurement time, and manpower. It is proven that the non‐contact method combining GPR with HHT is applicable to quickly and accurately measure stream cross section. Copyright © 2013 John Wiley & Sons, Ltd.     

Steady‐state analytical solutions of flow and deformation coupling due to a point sink within a finite fluid‐saturated poroelastic layer

An exact steady‐state closed‐form solution is presented for coupled flow and deformation of an axisymmetric isotropic homogeneous fluid‐saturated poroelastic layer with a finite radius due to a point sink. The hydromechanical behavior of the poroelastic layer is governed by Biot's consolidation theory. Boundary conditions on the lateral surface are specifically chosen to match the appropriate finite Hankel transforms and simplify the transforms of the governing equations. Ordinary differential equations in the transformed domain are solved, and then the analytical solutions in the physical space for the pore pressure and the displacements are finally obtained by using finite Hankel inversions. The analytical solutions at some special locations such as the top and bottom surfaces, lateral surface, and the symmetrical axis are given and analyzed. And a case study for the consolidation of a water‐saturated soft clay layer due to pumping is conducted. The analytical solution is verified against the finite element solution. Meanwhile, an analysis of coupled hydromechanical behavior is carried out herein. The presented analytical solution is an exact solution to the practical poroelastic problem within an axisymmetric finite layer. It can provide us a better understanding of the poroelastic behavior of the finite layer due to fluid extraction. Besides, it can be applied to calibrate numerical schemes of axisymmetric poroelasticity within finite domains. Copyright © 2017 John Wiley & Sons, Ltd.     

2000～2015年会理县地表覆盖变化监测

以LandSat多时相影像为数据源,采用基于规则的面向对象分类方法,监测会理县2000～ 2015年地表覆盖变化.结合1∶50 000 DEM数据,分析了会理县地表覆盖构成与转移、变化动态度及潜在退耕地情况.监测分析结论能为会理县加强空间管制、促进土地资源集约利用、指导生态文明建设等提供决策信息支撑.     

EMD-Wavelet-ICA耦合模型及其在GPS坐标序列降噪中的应用

在分析比较经验模态分解(EMD)、小波变换(Wavelet)和独立分量分析(ICA)优缺点的基础上,提出一种新的EMD-Wavelet-ICA耦合模型。该模型充分利用了EMD的自适应性,对原始信号进行分解获得不同频率的模态函数(IMF),采用标准化模量的累计均值对IMF进行尺度划分;进而分别采用Wavelet和ICA对高频和低频IMF进行降噪,将降噪后的IMF进行多尺度重构,获得降噪后的信号;采用信噪比、标准差、偏差和相关系数等指标对降噪效果进行评价。仿真数据和GPS坐标序列的处理结果表明:与EMD模型和EMD-ICA模型相比,新模型的标准差、偏差均有不同程度的减小;信噪比和相关系数有一定程度的增大,可以获得更好的降噪效果。     

求解GM(1,1)模型新总体最小二乘算法

在GM(1,1)模型中系数矩阵和观测向量都是由原始序列组成的。系数矩阵中同样是有误差的,与观测向量中的误差一样,亦来源于原始序列,即它们误差同源。不同位置的相同元素应该有相同的改正数,采用传统总体最小二乘求解则不能达到此目的。针对这一缺陷,推导了一种新的总体最小二乘算法;并且通过算例验证了新方法的可行性和有效性。     

从平衡-封闭-静态转向非平衡-开放-动力学研究-热液矿床成因的若干新概念概述

热液金属矿床成因研究过程中,观测与实验始终是密切结合的。上世纪70年代,平衡热力学的实验数据的快速积累,使人们用热力学理论计算可以预测和反演矿石和岩石的成因。但是,没有矿物-水溶液的反应速率数据,又没有与流体力学的结合,搞清楚矿石成因是困难的。七、八十年代,开始研究矿物与水溶液的反应动力学实验。科学家们开始瞄准了从平衡-封闭-静态转向非平衡-开放-动力学研究的这个大方向。1992年我们建立地球化学动力学开放研究实验室。研究高温高压矿物与水反应速率,发现固液的开放体系的自组织现象。实验发现温度影响矿物的各个元素反应速率改变,发现在跨越水临界态时矿物与水反应速率涨落、在近临界的气-液两相不混溶区一些金属进入气相、超临界流体的氧化作用及特别的溶剂性能影响矿物溶解性质。实验证实:临界态区流体与矿石成因有关。水岩相互作用的反应动力学实验温度从低温到550度,揭示矿石的金属来源、迁移、金属与蚀变分带机制。一大批大于300度的矿物与水反应动力学实验在国际界是少有报道的。九十年代,超高压的科学发展,与同步辐射光源的技术进步的结合,使固体地球科学又迈向了地球深内部。我们发展了高温高压流体性质的原位直测(测量850℃水溶液)红外谱,发现深部流体的新性质:气液两相流体的新结构,在临界温度区(300~400℃),水分子氢键网络的破坏受压力影响不大(23MPa~3GPa),同时,出现水的高电导率。研发新仪器为开放-流动-非平衡的反应动力学实验与极端条件下物质性质的直接观测结合,在科学前沿领域开辟了创新道路。