Rapid elemental analysis of sediment samples by isotope source XRF

Energy dispersive isotope-source X-ray fluorescence (XRF) analysers are little used in academic environmental research, in spite of being ideally suited to a number of tasks. In this paper an XRF method is tested by measuring a wide range of environmental materials of known elemental composition. Precision, accuracy and detection limits are presented.Using isotope-source X-ray fluorescence analysis, the total concentrations of Si, Ti, Ca, K, Fe, Mn, Cl, S, Nb, Ni, Pb, Rb, Sr, Zn and Zr can be determined in soils and sediments at a rate of >70 samples per day. The combination of speed and accuracy makes the technique ideal for three classes of application within environmental research. First, in sediments and soils that are highly heterogeneous, reliable characterisation is more dependent upon the number of samples measured than on measurement precision or accuracy. Under these circumstances the method is sufficiently accurate to be used alone. This is also the case where there is high and wide ranging contamination of sediment or soil by Pb and Zn. Second, major elements (Si, Ti, Fe, Ca, K and S) can be measured with sufficient accuracy in sediments and soils to aid the interpretation of other sediment chemical analyses. Third, the technique is ideal for the rapid screening of sediment or soil, allowing effective targeting of samples for more time consuming or expensive analyses. The XRF method presented here offers rapid, non-destructive total elemental analysis of sediments and soils that is sufficiently accurate to be useful in environmental research.     

Sequential sample reservoirs for Itrax-XRF analysis of discrete samples

Geochemical analysis of sediment samples can be used to characterize between- and within-lake variability and provide insights into lake chemistry, depositional processes and contamination sources. The number of samples for geochemical studies is restricted by cost, sample volume required, and the destructive nature of inductively coupled plasma mass spectrometry, instrumental neutron activation analysis, or wavelength dispersive x-ray fluorescence. Core scanners that incorporate energy dispersive x-ray fluorescence spectrometry, such as the Cox Itrax-XRF core scanner, have high through-put and can be used to produce high-quality geochemical datasets at low cost without destroying sample material. Here we describe a new analysis vessel that enables rapid, non-destructive Itrax-XRF analysis of discrete sediment samples.     

滤纸制样—X射线荧光光谱法测定卤水中的主量元素

采用滤纸制样,用X射线荧光光谱法对卤水中的钾钠钙镁硫进行测定。移取定量的卤水样品滴到已氟化锂环为底拖的滤纸上,再将滤纸和氟化锂环压制成型,上机测定。使用化学方法定值的卤水样品作为人工标准样品,建立校准曲线。本方法的准确度达到了化学分析的要求,相对标准偏差(RSD)6%,测量值与化学法结果吻合。     

XRF岩芯扫描分析方法及其在湖泊沉积研究中的应用

XRF岩芯扫描分析方法在海洋和湖泊沉积环境变化方面的应用研究,已取得了显著的成果,但在国内尚未见到研究成果的报道。XRF岩芯扫描分析方法具有快速、无破坏性、连续测试元素和对样品制备要求不高等特点,在获取高分辨环境记录方面更具独特的优势。因此,这一分析方法具有极好的应用前景,它能提高分析的准确性和精确度,加强高分辨率湖泊沉积与环境演变的整体性研究,促进环境指标的综合运用与定量化研究。从介绍XRF岩芯扫描分析方法的原理、特点、影响因素、分析结果的校正入手,进而分析该测试方法的应用现状与远景。     

Estimation of carbonate, total organic carbon, and biogenic silica content by FTIR and XRF techniques in lacustrine sediments

Major components of lacustrine sediments, such as carbonates, organic matter, and biogenic silica, provide significant paleoenvironmental information about lake systems. Fourier transform infrared spectroscopy (FTIR) and scanning X-ray fluorescence (XRF) techniques are fast, cost effective, efficient methods to determine the relative abundances of these components. We investigate the potential of these techniques using sediments from two large lakes, Lake Malawi in Africa and Lake Qinghai in China. Our results show statistically significant correlations of conventionally measured concentrations of carbonate (%CaCO₃), total organic carbon (%TOC), and biogenic silica (%BSi), with absorbance in the corresponding FTIR spectral regions and with XRF elemental ratios including calcium:titanium (Ca/Ti), incoherent:coherent X-ray scatter intensities (Inc/Coh), and silicon:titanium (Si/Ti), respectively. The correlation coefficients (R) range from 0.66 to 0.96 for comparisons of FTIR results and conventional measurements, and from 0.70 to 0.90 for XRF results and conventional measurements. Both FTIR and XRF techniques exhibit great potential for rapid assessment of inorganic and organic contents of lacustrine sediments. However, the relationship between XRF-ratios or FTIR-absorbances and abundances of corresponding sedimentary components can vary with sediment source and lithology.     

同步辐射加速器X荧光分析技术在北极气溶胶研究中的应用

本文应用同步辐射加速器X荧光(SR-XRF)分析技术并结合电感耦合等离子体质谱(ICP-MS)方法对中国首次北极考察采集的气溶胶样品进行了定量分析。SR-XRF方法对6种元素的分辨率分别为1.1ng/cm2(Ca)、39.7ng/cm2(V)、17.6ng/cm2(Fe)、2.3ng/cm2(Ni)、1.8ng/cm2(Zn)、6.4ng/cm2(Pb)。6种元素的浓度分别为117.3(ng/m3,Ca)、16.5(ng/m3,V)、19.3(ng/m3,Fe)、3.4(ng/m3,Ni)、4.5(ng/m3,Zn)、1.4(ng/m3,Pb)。该结果与文献报道的相应海区夏季气溶胶化学成分含量具有可比性。由于SR-XRF方法灵敏度高,属于无损分析,在极地气溶胶研究中具有广泛的应用前景。     

包头市表层土壤多元素分布特征及土壤污染现状分析

按4个/km2采集土壤样品,然后均匀混合形成一个组合的分析测试方式,在包头市研究区内共采集了884个土壤样品,组成了221个分析测试样品.分别用ICP-MS、XRF、GF-AAS和AFS法测定了土壤中34个元素的含量.通过对表层土壤多种元素含量分布特征的研究,表明:(1)该地区表层土壤富含Ca、Mg等碱土元素.(2)贫...     

预处理方法对重庆地区考古遗址粒度分析结果的影响

选取重庆石牛寺和大石洞考古遗址剖面,对比不同预处理方法对粒度测试结果的影响。研究表明：1)加蒸馏水浸泡或0.05 mol/L的(NaPO₃)₆分散剂,并用超声波震荡,分散效果均不明显,主要粒度参数与无预处理实验结果接近,表明物理性预处理方法既不能去除碳酸盐、有机质等杂质,也不能使样品中潜在的胶结团粒分散开。2)加H₂O₂可有效除去地层样品中的有机碎屑物,达到提纯无机颗粒物的目的。该方法预处理后,石牛寺考古遗址沉积物平均中值粒径最小,黏土体积分数最高,相比无预处理测试结果,砂体积分数降低50%左右,且在整个剖面中表现非常稳定;但对于大石洞遗址某些碳酸盐胶结物含量丰富的样品而言,该预处理方法作用有限。3)加10%稀HCl预处理后,石牛寺遗址样品中值粒径有所增大,砂体积分数基本持平,黏土体积分数显著降低,大石洞遗址黏土和砂体积分数同步减少,揭示黏土矿物可能在酸性环境下发生絮凝,从而导致体积分数减少。4)对于碳酸盐胶结物含量较低的环境考古样品,只需加H₂O₂除去有...     

同步辐射加速器X荧光分析技术在极地环境研究中的应用

本文简要介绍了同步辐射器X荧光(SRXRF)技术的分析原理和特点。概述了该技术在极地环境研究中的应用,并对其发展前景进行了展望。     

Preliminary investigation of mercury in bone tissues of skua and penguin in Antarctica using AFS and Synchrotron Radiation X-ray Fluorescence(SR-XRF)

<正> Mercury(Hg)was investigated in bone tissues of skua(Catharacta mac-cormick)and penguin(Pygoscelis adeliae)collected in the maritime Antarctic usingatomic fluorescence spectrometry(AFS)and synchrotron radiation X-ray fluorescence(SR-XRF)method.The total levels of mercury in bone tissues of penguin and skuaare much lower than those in other organs(e.g.,kidney,liver).The toxic effects ofmercury in bone tissues of seabirds in polar region are not known.We have used SR-XRF method to map the distribution of trace levels of mercury in bones.The levels ofmercury are found to be enriched somewhere near the periosteal surface and/or endos-teal surface.The distribution of mercury shows strongly correlation with that of someessential elements and probably poses negative effect on the bone metabolism inferringfrom the relationship of mercury with the other elements.These studies represent afirst step toward understanding the toxic effects of mercury on bone of polar animals bysuggesting the possible microscopic investigation.     

高碳铬铁EDXRF分析中的制样条件优化

利用能量色散X射线荧光光谱分析技术(EDXRF)检测高碳铬铁,能实现对主次组分的同时测量,且无需对铬铁样品进行化学处理.实验以荧光强度和测试精密度为指标,采用单因素试验考察了粉末压片制样过程中称样量、粘结剂种类与用量、研磨时间、压片压力、保压时间等制样条件对测量结果的影响趋势,并将优化后的条件用于对高碳铬铁的检测.结果...     

A protocol for preparing subfossil chironomid head capsules (Diptera: Chironomidae) for stable isotope analysis in paleoclimate reconstruction and considerations of contamination sources

Several techniques are available to examine the isotopic composition of historic lake waters, providing data that can subsequently be used to examine environmental changes. A recently-developed technique is the stable oxygen isotope analysis of subfossil chironomid (Diptera: Chironomidae) head capsules (mostly chitin) preserved in lake sediments. This technique involves a high Temperature Conversion Elemental Analyzer (TC/EA), which has been a relatively recent addition to the suite of online peripherals for analyzing the stable isotopic composition of organic samples. The highly precise and accurate ¹⁸O/¹⁶O and D/H measurements obtainable using the TC/EA with samples in the microgram range make this instrumentation suitable for studying geochemical and biological processes. Preparation of organic samples for isotopic analysis typically requires first weighing each sample into silver/tin capsules. These capsules can introduce oxygen and hydrogen contamination (a “blank effect”), which is especially problematic for analysis of small organic samples (e.g. less than 100 μg). Here we tested tin and silver capsules from two manufacturers and a range of sizes to assess contamination to small organic samples on the TC/EA. We also assessed how a method for cleaning silver capsules affected our analysis of commercial chitin. In general, capsules made of silver have less detectible oxygen than those made of tin, and capsules from the two manufacturers varied in their detectible oxygen. There was no detectable H contamination from silver capsules. In addition to our empirical findings, we present a model demonstrating the influence that contaminant oxygen can have on the δ¹⁸O of small organic samples. Sample mass becomes an important issue for such analyses. In light of our findings, we recommend a minimum sample mass ≥50 μg (approximately 120 whole chironomid head capsules) on a TC/EA-IRMS (Delta^plus XP system). Finally, we present a detailed protocol for preparing and transferring chironomid head capsules into silver capsules that minimizes the influence of contaminant oxygen. This protocol provides the paleo-community with another potential method for reconstructing paleoenvironments.     

基于X射线荧光光谱法测定少量样品的主次元素

在某些实验中,由于样品来源的有限性,导致样品数量有限,因而有必要探讨少量样品中主次元素的测定方法。X射线荧光光谱法具有样品制备简单、分析速度快、重现性好、测量范围宽和多元素同时进行分析的特点,目前在众多领域中得到了广泛的应用。基于回归曲线法、经验系数法和康普顿散射线内标法求取了各待测元素的工作曲线常数、元素间效应的影响系数和谱重叠系数,并对4 g(32 mm内径,常规)和1 g(10 mm内径,少量)样品测量的精密度和准确度进行了比较分析。结果表明,4 g(32 mm内径,常规)样品测量平均精密度约为1%,1 g(10 mm内径,少量)样品的平均精密度约为3%。测定结果基本能够满足覆盖区多目标地球化学调查样品的质量要求。     

基于电磁感应数据的膜下滴灌土壤水分动态变化研究

快速、无损监测农田土壤水分含量,是智慧农业的重要研究内容.以新疆南疆阿拉尔国家农业科技园区膜下滴灌棉田为研究对象,运用EM38-MK2大地电导率仪快速、高效的获取了4组不同时期的棉田土壤表观电导率数据,并同步采集表层土壤(0～20 cm)样品,通过构建表观电导率数据与室内测定含水量数据间的反演模型获取了测点的含水量数据...     

地统计法支持的北部湾东部海域沉积物粒径趋势分析

在北部湾东部海域采集表层沉积物71 个, 通过粒度分析获得其粒度参数(平均粒径、分选系数、偏态), 用克里格插值法将不规则采样站位的粒度参数内插为规则网格分布的相应粒度参数。采用地统计法分析其空间相关性, 计算度量空间相关性范围的参数, 即半方差图中的变程值。结果表明, 使用地统计分析获得的粒度参数变程值物理意义较为明确, 可作为粒径趋势分析模型的特征距离, 其中分选系数变程值作为特征距离的计算结果与前人的海流、沉积物输运信息更为吻合; 这在一定程度上消除了传统方法(试算法或经验估计法) 获取特征 距离可能造成的模型计算误差。采用不同间距插值时得到的粒径趋势矢量具有不同的空间分 辨率, 其中高分辨率的细化图所反映的海底沉积物净输运趋势与余流和环流等所反映的沉积物输运细节特征吻合较好, 低分辨率的概化图可大致反映该区域沉积物的总体输运趋势。地统计分析的结果对未来研究工作中采样间距的选取也具有指导意义。     

澜沧江河床沉积物重金属污染评价

河床沉积物是河流水体与泥沙环境中重金属的主要积存载体,能反映水环境的重金属污染状况。本文选取澜沧江为对象,通过对澜沧江干流西藏和云南境内22个河段的河床沉积物重金属测定分析,得到了8种主要的重金属元素(Cr、Mn、Ni、Zn、As、Pb、Cu和Co)的含量,并采用沉积物富集系数法与地质积累指数法分别对所测得沉积物的重金属污染程度进行了评价。结果表明:①澜沧江干流大部分河段污染情况并不明显,但在中游的旧州和功果桥河段,因该区域的地质金属背景值和支流沘江流域铅锌矿开采,地表的重金属元素被雨水冲刷到该河段,导致沉积物重金属富集现象明显,出现了轻度到较强度污染;②澜沧江流域受人为干扰的区域集中于中游与下游,部分河段(功果桥附近)Cu、Pb和Zn等元素呈轻度或偏中度污染;③大坝对河流的阻隔效应使得干流沉积物重金属污染呈现片段化分布,河流沿岸城市化等人类活动对附近河段沉积物重金属污染状况也有较明显的影响。     

一种基于地理环境相似度的滑坡负样本可信度度量方法

滑坡负样本在统计型滑坡危险度制图中具有重要作用,能抑制统计模型对滑坡危险度的高估。当前滑坡负样本采样方法采集的负样本可信度未知,在负样本采样过程中,极有可能将那些潜在滑坡点错选为负样本,这些假的负样本会降低负样本集的质量和训练样本集的质量,进而影响统计模型的精度。本文基于“地理环境越相似、地理特征越相似”的地理学常识,认为与正样本有着相似地理环境的点极有可能是未来发生滑坡的点;与正样本的地理环境越不相似的点,则越有可能是负样本。基于此假设提出一种基于地理环境相似度的负样本可信度度量方法,将该方法应用于滑坡灾害频发的陇南山区油房沟流域,对油房沟进行滑坡负样本可信度评价制图;使用油房沟流域的滑坡发生初始面来验证该方法的有效性。结果发现：滑坡发生初始面上所有栅格点的负样本可信度平均值为0.26,超过95%的栅格点的负样本可信度都小于0.5,说明本文提出的负样本可信度度量方法合理。     

Improving Coal Quality Estimations with Geostatistics and Geophysical Logs

In most modern coal mines, there are many coal quality parameters that are measured on samples taken from boreholes. These data are used to generate spatial models of the coal quality parameters, typically using inverse distance as an interpolation method. At the same time, downhole geophysical logging of numerous additional boreholes is used to measure various physical properties but no coal quality samples are taken. The work presented in this paper uses two of the most important coal quality variables—ash and volatile matter—and assesses the efficacy of using a number of geostatistical interpolation methods to improve the accuracy of the interpolated models, including the use of auxiliary variables from geophysical logs. A multivariate spatial statistical analysis of ash, volatile matter and several auxiliary variables is used to establish a co-regionalization model that relates all of the variables as manifestations of an underlying geological characteristic. A case study of a coal mine in Queensland, Australia, is used to compare the interpolation methods of inverse distance to ordinary kriging, universal kriging, co-kriging, regression kriging and kriging with an external drift. The relative merits of these six methods are compared using the mean error and the root mean square error as measures of bias and accuracy. The study demonstrates that there is significant opportunity to improve the estimations of coal quality when using kriging with an external drift. The results show that when using the depth of a sample as an external drift variable there is a significant improvement in the accuracy of estimation for volatile matter, and when using wireline density logs as the drift variable there is improvement in the estimation of the in situ ash. The economic benefit of these findings is that cheaper proxies for coal quality parameters can significantly increase data density and the quality of estimations.

     

Multifractal Modeling of Worldwide and Canadian Metal Size-Frequency Distributions

The Pareto-lognormal frequency distribution, which can result from multifractal cascade modeling, previously was shown to be useful to describe the worldwide size-frequency distributions of metals including copper, zinc, gold and silver in ore deposits. In this paper, it is shown that the model also can be used for the size-frequency distributions of these metals in Canada which covers 6.6% of the continental crust. Like their worldwide equivalents, these Canadian deposits show two significant departures from the Pareto-lognormal model: (1) there are too many small deposits, and (2) there are too few deposits in the transition zone between the central lognormal and the upper tail Pareto describing the size-frequency distribution of the largest deposits. Probable causes of these departures are: (1) historically, relatively many small ore deposits were mined before bulk mining methods became available in the twentieth century, and (2) economically, giant and supergiant deposits are preferred for mining and these have strongest geophysical and geochemical anomalies. It is shown that there probably exist many large deposits that have not been discovered or mined. Although overall the samples of the size-frequency distributions are very large, frequencies uncertainties associated with the largest deposits are relatively small and it remains difficult to estimate more precisely how many undiscovered mineral deposits there are in the upper tails of the size-frequency distributions of the metals considered.