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.     

Water soluble components of PM10 Chongqing, China

The concentrations of water soluble ions (Na⁺, NH₄ ⁺, K⁺, Mg²⁺, Ca²⁺, NO₃ ^-, Cl^-, and SO ₄ ^2- ) in PM₁₀ samples collected on cellulose filters by a medium-volume cascade impactor were determined, which were obtained from three kinds of areas in Chongqing: industrial area (Jiulongpo district), commercial and residential area (Jiangbei district) and background area (Jinyun Mountain in the Beibei district). The results showed that except for the background site, the annual average values of PM₁₀ are 23% – 61% higher than the national air quality standard (GradeII) (0.1 mg/m³), even that the value of the control site is still 20% higher than American standard (0.05 mg/m³). This implied that serious pollution of fine particles occurred in Chongqing. Nine kinds of soluble ions in water of PM₁₀ were analyzed by ion chromatography (IC) and the annual average concentrations follow the order of [SO ₄ ^2- ] > [NO³ _-] > [Cl^-] > [F^-], and [Ca²⁺] > [NH₄ ⁺] > [K⁺] > [Na⁺] > [Mg²⁺]. Their values were different in these areas: the industrial area > the commercial and living area > the control area. As for NH_{4 +}, K⁺, Ca²⁺, NO₃ ^- and SO ₄ ^2- , their seasonal average concentrations show a similar variation trend: the values in spring and fall were higher than those in summer and winter. The seasonal average concentrations of [Cl^-], [F^-], [Na⁺] and [Mg²⁺] are much lower than those of other ions. However, the concentrations of [Na⁺] changed more greatly in different seasons than those of the other three ions. Correlation coefficients showed that the three areas have been polluted by coal smoke and dust to different extents, while some local resources of pollution should be taken into consideration as well.     

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.     

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.     

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。     

南水北调中线突发水污染事件的快速预测

依据南水北调中线干渠资料,开展了正常输水情况下串联明渠内可溶污染物浓度分布规律数值模拟研究。采用数值模拟、数学归纳和统计分析方法,提出表征污染物输移扩散特征的峰值输移距离、污染带长度和峰值浓度的快速预测公式;通过示范工程验证了快速预测公式的可行性。结果表明:①串联明渠内,峰值输移距离随渠道流速减小而减小,并且污染带长度增加值随明渠内流速减小而减小,但是峰值浓度随明渠流速减小而增加;②快速预测公式计算结果与现场试验实测结果的误差均不到15%,证明了快速预测公式的合理性和可行性。这些研究结果为南水北调中线工程突发可溶性水污染事件应急预警方案的制定提供了科学依据。     

A new assessment model for evacuation vulnerability in urban areas

In the high-speed urbanization process of China, the urban population has been increasing significantly, leading to a high-density aggregation of population. However, the sharp increase in population density has not produced commensurate improvements in the road networks. On the contrary, the population increase induced a serious evacuation vulnerability, which cities experience during various hazards and catastrophic events. Therefore, research on evacuation vulnerability is important to urban planning. To assess the evacuation vulnerability, the optimal and worst scenarios should be considered because all possible evacuation plans occur between these extremes. However, most previous evacuation vulnerability studies are based on the worst-case scenario, only providing an upper bound of a potential evacuation assessment. To provide a more comprehensive theoretical basis for decision-makers to understand the consequences caused by all possible evacuations, this paper proposes an optimal evacuation vulnerability assessment model that provides the lower bound on potential evacuation difficulties. The model is solved by a stepwise spreading algorithm based on Graph Theory. Subsequently, to evaluate the effectiveness of the model, the study adopts the model to assess the evacuation capability of different road network topologies. A comparison with previous research was performed. The model was demonstrated in an application to the South Luogu Alley of Beijing, China. The significance of this paper is that the combination of our model with previous research may provide a more complete theoretical basis for an evacuation vulnerability assessment.     

A New Reference Material for Tritium Organic Molecules in Sediment: Results of an International Intercomparison Exercise

Solid matrix ³H reference materials are challenging to prepare given the volatile nature of ³H and are often unrepresentative of the range of ³H forms that may be encountered during routine analysis. As a result, few ³H reference materials are currently available, undermining verification of analytical techniques for environmental ³H measurement. To address this, an International Working Group on Organically‐Bound Tritium Analysis determined to produce a tritium natural matrix reference material (NMRM). The reference material comprises marine sediment blended with sewage sludge contaminated with ³H‐organic species arising from authorised discharges from a radiopharmaceutical manufacturing site. Previous studies have demonstrated that the ³H species have persisted in the environment over three decades providing valuable supporting data to underpin the characterisation of the NMRM. The preparation and characterisation of the NMRM are described along with the subsequent application of the reference material in an international intercomparison exercise involving nineteen laboratories from nine countries. A reference value of 168 ± 22 Bq kg^?1 was derived from the data arising from the proficiency test.     

微波等离子体原子发射光谱法测定偏远矿区海泡石中的主微量元素

海泡石是具有层状结构的含水富镁硅酸盐黏土矿物,其中无机元素含量是揭示其成矿物质来源、成矿流体性质和矿床成因的重要依据,通常采用电感耦合等离子体发射光谱/质谱法(ICP-OES/MS)进行测定,等离子体(ICP)的高温激发会产生成大量谱线干扰,维持ICP稳定工作需使用高纯氩气,持续供气对于偏远矿区海泡石的检测还将面对气体采购和运输不便的问题。本文基于微波等离子体原子发射光谱(MP-AES)的低温激发技术减少光谱干扰,建立了准确测定偏远矿区海泡石中主量元素Mg、Al、Ca、Fe、K、Na和微量元素Cu、Zn、Mn、Pb含量的分析方法。利用硝酸-盐酸-氢氟酸混合酸对海泡石进行微波消解,避免了样品处理过程中分析元素的损失,加快了样品处理速度,同时提高了样品溶液的稳定性。通过选择各元素光谱线的分析波长,并利用快速线性干扰校正(FLIC)技术校正光谱干扰,以Lu为内标元素校正基体效应,提高了灵敏度和准确度。各元素的检出限为0.19～14.6μg/L。海泡石国家标准物质(GBW07138)各元素测定值与认定值的相对误差在-5.0%～6.7%之间。本方法具有检出限低、线性范围宽、结果准确等优点;MP-AES采用自带的氮气发生器为等离子体提供氮气作为工作气,无需引入复杂气体,提高了分析效率,尤其适用于气体采购和运输不便的偏远矿区。