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。结果表明,使用6 g样品和0.4 g微晶纤维素,研磨时间为3 min,压片压力为40 MPa,保压时间为1 min时制得的样片表面光滑,测定重现性好。精密度和稳定性分析表示,各元素测定结果的相对标准偏差(RSD)均小于0.5%,证明优化制样条件后可以满足利用EDXRF定量分析铬铁主次元素的要求。     

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。     

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。     

X射线衍射在盐湖研究中的应用

对X射线衍射仪的工作原理、物相定性、定量分析方法进行了扼要介绍,同时详细论述了X射线衍射仪在盐湖地质(盐类矿物、盐湖粘土矿物、盐湖沉积矿物与古气候古环境关系)、盐湖化工(镁水泥、锂离子电池和晶须材料)和水盐体系相图研究中的应用。     

拉果错盐田中三方硼砂的发现及成因

拉果错盐湖位于西藏自治区阿里地区改则县麻米乡境内,盐湖水化学类型为硫酸钠亚型,氯化锂资源储量232×10⁴t,是西藏重要锂盐湖之一。前人对拉果错盐湖的研究集中在锂元素来源、成矿规律,不同温度下盐类矿物析出序列等,对盐湖中含硼盐类矿物并未开展相关研究。对拉果错盐田中采集的5件样品进行X射线衍射实验和扫描电镜分析,发现盐田中盐类矿物组合为三方硼砂、石盐、钾石盐、钾芒硝、无水芒硝、硫酸锂钾。三方硼砂呈他形—半自形的短柱状集合体,长约36 μm,宽约30 μm,含量在5.94%~84.51%,为硼砂脱水的次生成因,属硫酸盐型盐湖中首次发现。     

西藏拉果错盐田中三方硼砂的发现及成因

拉果错盐湖位于西藏阿里地区改则县麻米乡境内,盐湖水体类型为硫酸钠亚型地表卤水,氯化锂资源储量232万吨,是西藏重要锂盐湖之一。前人对拉果错盐湖的研究集中在锂元素来源、成矿规律,不同温度下盐类矿物析出序列等,对盐湖中含硼盐类矿物并未相关研究。本次工作对拉果错盐田中采集的5件样品进行X射线衍射实验和扫描电镜分析,发现盐田中盐类矿物组合为三方硼砂、石盐、钾石盐、钾芒硝、无水芒硝、硫酸锂钾。三方硼砂呈他形-半自形的短柱状集合体,长约36μm,宽约30μm,含量在5.94%-84.51%。三方硼砂为首次在硫酸盐型盐湖卤水盐类结晶矿物中被发现,由先析出的硼砂脱水形成,属次生三方硼砂。     

西藏扎布耶盐湖太阳池中富锂混盐的矿物学与地球化学特征及意义

扎布耶盐湖是全球最独特的自然结晶扎布耶石(Li2CO3)的盐湖。该盐湖正在开发利用中,2020年产富锂混盐4500吨。实验所采取的样品是通过“盐梯度太阳池”技术结晶出来的10件富锂混盐。通过对采集的样品进行X射线衍射、扫描电镜、电感耦合等离子质谱法、离子色谱法和滴定法的测试,得到了矿物组成的成分和化学元素组成含量数据,扎布耶盐湖太阳池富锂混盐中的物相组成有扎布耶石、钾石盐、石盐、氯碳钠镁石、天然碱、钾芒硝、菱锰矿、石英这8种,其中菱锰矿是首次从富锂混盐中发现的矿物,扎布耶石的含量为24.10%-88.27%,平均为62.89%,是该盐湖中含量最高的矿物。测试的样品中Li含量4.56%-16.70%,平均为11.90%；K+含量为0.14%-10.17%,平均为2.42%； KCl的含量为0.26%-20.44%,平均为4.63%(工业品位1%)。该混盐的结构和构造的形成受温度和水流的影响,温度越高碳酸锂的结晶速率越快,碳酸锂的晶核生长速率和晶粒大小与温度呈正相关。扎布耶盐湖二期工程预计年产20000吨碳酸锂,其中利用膜法生产12000吨；利用太阳池技术生产8000吨,预计年产出12700吨的富锂混盐,可以产出约600吨氯化钾,建议进行综合利用。     

粉末压片——X射线荧光光谱线性扫描在岩石矿物全分析中的应用

本论文提出用粉末压片X射线荧光光谱线性扫描法进行未知样品无标样测定,通过与经典方法测试结果计算相对偏差和相对允许偏差的合格率,表明其检测结果的准确,使用该方法进行全分析比经典方法更准确更效率。     

南极菲尔德斯半岛六种藻类和地衣植物的X荧光分析

为了研究南极的植物与环境间的关系 ,探讨植物在南极环境监测中的作用 ,在无标样条件下 ,利用微束 X荧光分析法对南极菲尔德斯半岛的 6种藻类和地衣植物进行了元素分析。其中藻类植物有孔石莼 (Ulva pertusa)、海膜 (H alymenia sp.)和大型鞘丝藻 (Lyngbya major) ,地衣植物有筛石蕊 (Cladonia borealis)、喇叭石蕊 (C.fimbriata)和松萝 (Usnea sp.)。研究结果发现 ,不同的藻类植物对各种元素的吸收能力不同 ,在 XRF(X射线荧光 )谱中 ,孔石莼比海膜含有更多的元素 ,象 As、Br和 Rb,Cu和 Zn的含量也较高。在大型鞘丝藻中 ,K比 Ca少 ,Zn的含量较高。在 3种地衣植物中 ,其 XRF谱中的元素种类组成非常相似 ,只是 Mn、Fe、Cu和 Zn等元素的相对含量有些差异     

荒漠地区15种植物的元素含量

采集了15种荒漠地区常见植物的样品，基于X射线荧光光谱法对其元素含量进行了测定。结果表明：组成荒漠地区植物的常量元素主要有Cl、S、P、Ca、Si、Al、K、Na和Mg，微量元素主要有Sr、Rb、Br、Zn、Cu、Ni、V、Ti、Ba、Mn 和Fe。不同种类植物中各元素的含量不同，体现了植物因遗传生理特性的不同而对环境元素选择吸收的特点。15种荒漠植物的常量元素组成的典型特征是富Ca、K贫Na，表明生境对各类植物化学成分含量的统一影响。属于同科的植物化学元素组成比较接近，说明植物元素化学成分可作为植物分类的标志之一。     

塞曼石墨炉原子吸收法测定地球化学样品中银元素

对塞曼效应石墨炉原子吸收法对地质样中痕量银的测定进行了研究。简化了样品处理过程。对地质标样及实际样品分析获得了满意的结果加标回收率为96.2%-103.5%,相对标准偏差为3.04%-4.77%所采用的方法快速、简便,准确。     

Wavelength dispersive X-ray fluorescence spectroscopy as a fast,non-destructive and cost-effective analytical method for determining the geochemical composition of small loose-powder sediment samples

X-ray fluorescence spectroscopy (XRF) has been used extensively to analyze many types of environmental samples, including lake sediments. In most cases, however, analyses have required either a relatively large sample mass or sample pretreatment, e.g. lithium borate fusion, and have not taken advantage of the potential of XRF analysis as a non-destructive technique. This paper describes the development of two completely non-destructive calibration methods that use small, i.e. 200- and 500-mg loose-powder sediment samples. Analytical performance of these methods was assessed using ten different certified reference materials and a previously analyzed sediment profile, and for both methods, accuracy and precision were less than ±10 % (or a few ppm) for 26 elements (Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Mn, Fe, Ni, Cu, Zn, Ga, As, Br, Rb, Sr, Y, Zr, Sn, Sb, Ba, W and Pb). This shows that quantitative wavelength dispersive X-ray fluorescence analysis, using small loose-powder samples, can be a useful geochemical tool for many paleolimnological applications, especially because lack of pretreatment ensures that samples can be used for further analysis.     

A modified method for biogenic silica determination

We describe a modified method for the determination of biogenic silica (BSi) in lacustrine sediment samples with BSi concentrations >0.5% SiO₂ (detection limit). To speed up the leaching procedure (48 samples per day), we suggest the use of Teflon autoclaves that can be left unattended (no stirring of the solution) for 3 h at 100°C in an oven. We suggest a volume correction by Na measurement to account for volume errors during pipetting off a hot solution. We also propose to carry out a correction for minerogenic silica by the simultaneous determination of Al in the leachate. Analytical precision and accuracy of the proposed method are 2.4% (relative standard deviation) and 70–110% recovery (relative to the mean of four international reference sediment samples), respectively. Additionally, we demonstrate that pre-treatment of the samples with H₂O₂ and/or HCl prior to alkaline leaching is not necessary for all samples. Due to the great diversity of lacustrine and marine sediments, however, the pre-treatment procedure should be tailored for samples from different sites.     

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.     

INVESTIGATING MORPHOLOGICAL CHARACTERISTICS AND CHEMICAL COMPOSITION OF NAFTLIGE MUD VOLCANO IN GOLESTAN PROVINCE,EASTERN PART OF THE CASPIAN SEA

Mud volcanoes are geomorphological phenomena and there is a limited volume of knowledge about them. Output of a composition of water, mud, and gas forms the mud volcano phenomenon. Geographical distribution of mud volcanoes indicates their relationship with pressured, rapid and thick sedimentation, which is seen in both tectonically active and inactive zones. Naftlige mud volcano is located in the southwest of the Caspian Sea and west of Gomishan Wetland in Golestan Province, Iran. Since no study has ever been conducted with a specific focus on mud volcanoes, field and laboratory studies were carried out for the first time to overcome the shortage of library resources. The objective was to determine the composition of emerging mud and study its morphometric and geomorphic features so that there would be a method for identifying and introducing some unknown aspects of this mud volcano. Therefore, three samples of this mud volcano which were taken on 27 Apr., 2012 were tested and analyzed using X‐ray diffraction and X‐ray fluorescence techniques to determine the mineral and chemical composition. The results of this analysis showed that, in these three samples, silicon oxide with the chemical formula SiO₂ had 40.88% volatile materials, 19.15% H₂O Loss on Ignition (LOI) and 13.97% calcium oxide. Quartz, calcite and albite formed the three main phases of minerals.     

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.     

Estimation of grain size variability with micro X-ray fluorescence in laminated lacustrine sediments,Cape Bounty,Canadian High Arctic

Finely laminated sediment cores from two Arctic lakes were investigated using the Itrax™ Core Scanner that provides micro X-ray fluorescence (μ-XRF) measurements with a spatial resolution of 100 μm. We compared these chemical measurements with standard geochemical methods using, at the macroscopic scale, inductively coupled plasma–atomic emission spectrometry (ICP-AES) and, at the microscopic scale, energy dispersive spectroscopy (EDS). We also investigated the relationship between the chemical profiles and the grain size of sediments at macro-scale using laser particle-size analysis, and at microscopic scale, using thin section image analysis techniques. Results show a link between grain size and the relative abundance of several elements. Silicon and zirconium are associated with very coarse silt and sand deposits, K and Fe with clay-rich layers, and Ti with silty facies. Four sedimentary facies are characterised based on sedimentary structure and texture, and interpreted in terms of known seasonal hydroclimatic processes. We show that is possible to identify these sedimentary facies using μ-XRF element abundance or ratio variations. The K/Ti ratio is the best marker of the upper varve boundary, and it might be used for varve identification and counting of Cape Bounty sediments in future. More generally, this study demonstrates new applications for paleohydrological reconstructions from laminated sediments.     

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.