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.     

Development of a rain‐on‐snow detection algorithm using passive microwave radiometry

Currently observed climate warming in the Arctic has numerous consequences. Of particular relevance, the precipitation regime is modified where mixed and liquid precipitation can occur during the winter season leading to rain‐on‐snow (ROS) events. This phenomenon is responsible for ice crust formation, which has a significant impact on ecosystems (such as biological, hydrological, ecological and physical processes). The spatially and temporally sporadic nature of ROS events makes the phenomenon difficult to monitor using meteorological observations. This paper focuses on the detection of ROS events using passive microwave (PMW) data from a modified brightness temperature (T_B) gradient approach at 19 and 37 GHz. The approach presented here was developed empirically for observed ROS events with coincident ground‐based PMW measurements in Sherbrooke, Quebec, Canada. It was then tested in Nunavik, Quebec, with the Advanced Microwave Scanning Radiometer for the Earth Observing System (AMSR‐E). We obtained a detection accuracy of 57, 71 and 89% for ROS detection for three AMSR‐E grid cells with a maximum error of 7% when considering all omissions and commissions with regard to the total number of AMSR‐E passes throughout the winter period. Copyright © 2016 John Wiley & Sons, Ltd.     

激发极化法在辽宁本溪某矽卡岩型铜多金属矿勘查中的应用

测区燕山期大面积中酸性岩浆侵入寒武系、奥陶系碳酸盐岩,在岩体外接触带上形成大量的矽卡岩,并伴有较强烈的铜多金属矿化。本次物探工作在1∶5万区调工作基础上,采用激电中梯与激电测深两种方法进行金属矿产勘查,圈定激电异常12个,反演了穿过JD3、JD7、JD8高极化异常体的形态,规模及埋深,并解译隐伏断裂2条。结合区内地质特征与钻孔资料,认为异常区的低阻高极化体是岩体外接触带上矽卡岩化蚀变带的反映,断裂为矿液运移、容矿提供了有利条件。该研究成果表明,激发极化法是寻找矽卡岩型铜多金属矿的有效方法。     

Impact of sub-pixel heterogeneity on modelled brightness temperature for an agricultural region

Knowledge of sub-pixel heterogeneity, particularly at the passive microwave scale, can improve the brightness temperature (and ultimately the soil moisture) estimation. However, the impact of surface heterogeneity (in terms of soil moisture, soil temperature and vegetation water content) on brightness temperature in an agricultural setting is relatively unknown. The Soil Moisture Active Passive Validation Experiment 2012 (SMAPVEX12) provided an opportunity to evaluate sub-pixel heterogeneity at the scale of a Soil Moisture Ocean Salinity (SMOS) or the Soil Moisture Active Passive (SMAP) radiometer footprint using field measured data. The first objective of this study was to determine if accounting for surface heterogeneity reduced the error between estimated brightness temperature (T_b) and T_b measured by SMOS. It was found that when accounting for variation in surface soil moisture, temperature and vegetation water content within the pixel footprint, the error between the modelled T_b and the measured T_b was less than if a homogeneous pixel were modelled. The correlation between the surface parameters and the error associated with not accounting for surface heterogeneity were investigated. It was found that there was low to moderate correlation between the error and the coefficient of variance associated with the measured soil moisture, soil temperature and vegetation volumetric water content during the field campaign. However, it was found that the correlations changed depending on the stage of vegetation growth and the amount of time following a precipitation event. At the start of the field campaign (following a precipitation event), there was strong correlation between the error and all three surface parameters (r ≥ 0.75). Following a precipitation event close to the middle of the field campaign (during which there was rapid growth in vegetation), there was strong correlation between the error and the variability in vegetation water content (r = 0.89), moderate correlation with soil moisture (r = 0.61) and low correlation with soil temperature (r = 0.26).     

电感耦合等离子体质谱法(ICP-MS)测定水系沉积物中的铌钽锆铪

建立电感耦合等离子体质谱法(ICP-MS)测定水系沉积物中铌、钽、锆、铪四种元素的分析方法。将样品与氢氧化钠、过氧化钠混合物放入高温炉中,熔融分解完全,用热水提取,过滤后弃去滤液,将滤纸及沉淀用酒石酸-盐酸溶液溶解,稀释至刻度测定。方法检出限(3s)为:LD(Nb)=0.08μg/g,LD(Ta)=0.04μg/g,LD(Zr)=0.5μg/g,LD(Hf)=0.04μg/g,精密度(RSD%,n=6)为:0.84%~4.21%。该测定方法具有灵敏度高、精密度好、分析速度快、线性范围宽、操作性强等优势。采用该方法对国家一级标准物质进行测定表明,其结果与标准值吻合。此方法已在实际地质调查样品分析中得到应用。     

荆江三口分流变化及三峡水库蓄水影响

长江中游荆江的水沙通过三口洪道分流入洞庭湖,三口分流是荆江-洞庭湖关系调整的驱动因子,为揭示其变化特征及三峡工程运用的影响,基于大量的原观数据,系统研究了近60年三口分流比的变化过程,提出其显著调整特征及诱发因素,引入径流还原计算方法,量化了三峡水库不同运用方式对三口分流量的影响幅度。结果表明:①特大洪水及重大人类活动等诱发因素作用下,三口分流比出现4~5年持续性减小的趋势调整期,之后进入分流比稳定恢复的平衡调整期;②2003-2014年,三峡水库汛前枯水补偿调度使得三口分流量年均增加8.000亿m3,汛后蓄水使得三口分流量年均减小29.00亿m3,对三口分流综合影响量为年均减少21.00亿m3,占同期三口年均分流量的4.29%。     

An Investigation of Digestion Methods for Trace Elements in Bauxite and Their Determination in Ten Bauxite Reference Materials Using Inductively Coupled Plasma‐Mass Spectrometry

Trace elements from samples of bauxite deposits can provide useful information relevant to the exploration of the ore‐forming process. Sample digestion is a fundamental and critical stage in the process of geochemical analysis, which enables the acquisition of accurate trace element data by ICP‐MS. However, the conventional bomb digestion method with HF/HNO₃ results in a significant loss of rare earth elements (REEs) due to the formation of insoluble AlF₃ precipitates during the digestion of bauxite samples. In this study, the digestion capability of the following methods was investigated: (a) ‘Mg‐addition’ bomb digestion, (b) NH₄HF₂ open vessel digestion and (c) NH₄F open vessel digestion. ‘Mg‐addition’ bomb digestion can effectively suppress the formation of AlF₃ and simultaneously ensure the complete decomposition of resistant minerals in bauxite samples. The addition of MgO to the bauxite samples resulted in (Mg + Ca)/Al ratios ≥ 1. However, adding a large amount of MgO leads to significant blank contamination for some transition elements (V, Cr, Ni and Zn). The NH₄HF₂ or NH₄F open vessel digestion methods can also completely digest resistant minerals in bauxite samples in a short period of time (5 hr). Unlike conventional bomb digestion with HF/HNO₃, the white precipitates and the semi‐transparent gels present in the NH₄HF₂ and NH₄F digestion methods could be efficiently dissolved by evaporation with HClO₄. Based on these three optimised digestion methods, thirty‐seven trace elements including REEs in ten bauxite reference materials (RMs) were determined by ICP‐MS. The data obtained showed excellent inter‐method reproducibility (agreement within 5% for REEs). The relative standard deviation (% RSD) for most elements was < 6%. The concentrations of trace elements in the ten bauxite RMs showed agreement with the limited certified (Li, V, Cr, Cu, Zn, Ga, Sr, Zr and Pb) and information values (Co, Ba, Ce and Hf) available. New trace element data for the ten RMs are provided, some of which for the first time.     

圆回线和矩形回线源瞬变电磁响应差异性计算

在回线源瞬变电磁发展的早期,往往使用圆回线产生的场来近似模拟多边形回线的场。为了对这种近似的影响进行分析,本文以矩形回线为例,对圆回线近似模拟多边形回线的误差进行计算。首先,根据给出的圆回线和矩形回线内外任一点的感生电动势新的计算方法,对两种回线装置内的感生电动势分布进行对比。研究结果表明:在扩散场早期,圆回线和矩形回线场的等值线分布形态存在较大的差别,而在扩散场中晚期,两种回线感生电动势相对误差较小。两种回线感生电动势相对误差的变化特征可以用感应电流烟圈扩散的理论进行解释。通过理论模型的分析可知,圆回线近似矩形回线会对浅层电性结构分析带来较大影响。     

微波消解-电感耦合等离子体质谱法测定海泡石中的稀土元素

海泡石是一种纤维状含水的富镁硅酸盐黏土矿,其中的稀土元素含量在1×10~(-7)～1×10~(-5)之间,目前还没有建立海泡石中稀土元素的国家标准分析方法。测定岩石中的稀土元素主要是采用电感耦合等离子体质谱法(ICP-MS),样品前处理一般采用封闭溶矿和碱熔,但这两种处理方法耗时较长,效率不高。本文通过比较硝酸-氢氟酸-过氧化氢、硝酸-氢氟酸、硝酸-过氧化氢三种样品前处理方法,确定使用硝酸-氢氟酸溶矿,然后进行微波消解同时赶去氢氟酸,避免氢氟酸与稀土元素生成难溶的氟化物,再采用ICP-MS法测定15种稀土元素的含量。由于海泡石中的镁含量较高,为降低基体效应,以~(103)Rh和~(185)Re作内标补偿基体效应和校正灵敏度漂移,各元素测定值的准确性显著提高,回收率为91. 2%～110. 9%,检出限为0. 002～0. 011μg/L,精密度≤2. 79%。本方法与封闭酸溶ICP-MS法的分析结果吻合较好,且用酸量少(7 mL),溶矿效率高(1 h),检出限更低。     

2000-2014年西藏雅鲁藏布江流域积雪时空变化分析及对气候的响应研究

利用2000-2014年MODIS逐日无云积雪产品对雅鲁藏布江流域积雪特征的空间分布及变化、积雪随高程变化的规律进行了分析,并采用被动微波数据SMMR （1979-1987年）和SSM/I （1988-2008年）以及中国地面降水和气温0.5°×0.5°日值格点数据集,研究了雅鲁藏布江流域关键积雪参数对气候要素的响应等。结果表明：流域下游积雪日较大且变化剧烈;流域整体上呈显著减少的趋势;积雪日随高程的上升而增加;流域内降水呈不显著的增加趋势,而气温呈显著的增加趋势,最高气温对积雪变化影响最大;气温对积雪终日的影响明显高于积雪初日;在积雪消融期降水的增多促进了积雪的消融。