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    20 June 2021, Volume 27 Issue 3
    Research Progress of Geochemistry in Tungsten Deposit: Based on the Wolframite U-Pb, Sm-Nd, Lu-Hf Isotope Geochronlogy and Trace Element Characterics
    YANG Ming, WANG Hao , WU Shitou, YANG Yueheng
    2021, 27(3):  250-263.  DOI: 10.16108/j.issn1006-7493.2021030
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    Wolframite occurs as one of the main ore minerals in tungsten deposit. It is more effective to directly date wolframite to represent its mineralization age. Since it usually contains a certain amount of U and some samples exhibit high Sm/Nd ratios, thus, wolframite U-Pb and Sm-Nd dating methods have been applied to the metallogenic chronology study of various wolframite deposits. However, wolframite U-Pb and Sm-Nd dating methods have their own limitations, so the dating is commonly unsuccessful or the results are not ideal. In this paper, we systematically reviewed and analysed the development of wolframite U-Pb and Sm-Nd dating methods, and discussed the challenges and opportunities of wolframite U-Pb and Sm-Nd chronology. Meanwhile, we also evaluated the application prospect of wolframite Lu-Hf chronology in the light of the published Lu and Hf data of wolframite. It has been shown that the Lu/Hf ratio in wolframite has a large variation range and that Lu-Hf dating method is of great potential. This paper discussed the existing problems and possible solutions of wolframite geochronology in defining the mineralization age of tungsten deposit, in order to promote the development of wolframite geochronology in the future.

    High Precision Analytical Method for Stable Strontium Isotopes
    CHEN Xuqi, ZENG Zhen, YU Huimin, HUANG Fang
    2021, 27(3):  264-274.  DOI: 10.16108/j.issn1006-7493.2021031
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    Because of the development of high-precision stable Sr isotope analytical method, stable Sr isotopes have been paid more attention in recent years. Great progress has been made in studies on supergene geochemistry, paleoenvironment, archaeology, endogenesis, and meteorites. This paper summarizes the key techniques of δ88/86Sr analytical methods. Ion exchange method with Eichrom Sr Specific Resin has been widely used to purify Sr. But this specific resin is expensive and may result in contamination during the chromatographic processes. Thus it could be replaced by cation-exchange resin. MC-ICP-MS and TIMS are the instruments for isotope measurement. Normally, MC-ICP-MS has higher measurement efficiency but slightly lower precision than TIMS. Standard-Sample-Bracketing method, Zr-Empirical-External-Normalization method, and double spike method are used to correct the instrumental mass bias. The Double Spike method may have relatively high measurement precision, but there are only a few studies using this method on MC-ICP-MS. Furthermore, there is no detailed comparison of δ88/86Sr of international standard materials. Therefore, optimizing the analysis process, improving the measurement precision, and more determination of δ88/86Sr of standard materials are necessary for the future studies of stable Sr isotopes.

    Progress in High Precision Analytical Approaches of Silicon Isotope
    WANG Junlin, WANG Wei, WEI Haizhen
    2021, 27(3):  275-288.  DOI: 10.16108/j.issn1006-7493.2021033
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    With the modification of Alkali fusion method for digesting silicates and the development of the multi-collection inductively coupled plasma mass spectrometer (MC-ICP-MS), the silicon isotopic analysis methods have been significantly improved in recent years. The analytical precision of δ30Si (2SD) is better than ±0.10‰, compared with ±0.15‰-±0.30‰ by gas mass spectrometer (GS-MS) in earlier studies. It enables us to distinguish the minor fractionation of Si isotopes during the
    high temperature processes; and also avoid using hazardous chemical such as fluoride. For the in situ determination of δ30Si, the analytical precision of secondary ion mass spectrometry (SIMS) and femtosecond laser ablation (fs LA) also have been modified to be ±0.10‰-±0.22‰. This article reviewed the progress in silicon isotope analysis in the past decades, and discussed the establishment of high precision silicon isotope analysis method under wet plasma condition using MC-ICP-MS. Then we compared the silicon isotopic compositions of standard reference materials in different laboratories, and finally summarized the range of δ30Si in major geological reservoirs, e.g., BSE, Earth crust and Meteorites.

    A Review of Barium Isotope Analytical Methods
    TIAN Lanlan, YU Huimin, NAN Xiaoyun, HUANG Fang
    2021, 27(3):  289-305.  DOI: 10.16108/j.issn1006-7493.2021032
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    With the advancement of analytical techniques and the development of mass spectrometers (MC-ICP-MS and TIMS), the barium isotopic analysis methods have been significantly improved. The analytical precision of δ138/134Ba is better than 0.05 ‰ (2SD) compared with 1 ‰ (2SD) in previous studies. This article reviewed the barium isotope analysis methods (solution methods) in the past ten years, and summarized the digestion methods, the chemical purification procedures, and the instrumental analysis of barium isotopes for different types of samples. In addition, the barium isotopic compositions of various reference materials analyzed in different laboratories are summarized in this study. We hope that this paper will help researchers to establish in situ analysis methods of Ba isotopes, and also provide support in Ba isotope fractionation mechanism deduction and geological applications.
    Several Perspectives on Microprobe Trace Elements Analysis
    LI Xiaoli
    2021, 27(3):  306-316.  DOI: 10.16108/j.issn1006-7493.2021034
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    Electron Probe Micro Analyzer (EPMA) is a quick, non-destructive and in-situ technique with high precision, accuracy and sensitivity that is very powerful in micro domain chemical analyses. It is a fundamental research method in modern sciences.
    EPMA quantitative analysis acquires element abundance in “quantity” instead of any “weight” or “mass” reflection, thus, it is
    more appropriate to use atom proportion and/or atom ratio to examine the result’s correctness, but not simply depend on the mass total in the range of 100±2 wt%. The trace element in material (mineral) is of great importance as a typomorphic indicator for particular (geologic) genetic environment, which serves a key research subject in material science. EPMA is the best approach in (in-situ) analyzing trace elements considering its performance advantages. However, in practice, the trace element measurement often faces various technical difficulties with several unavoidable flaws, particularly with wavelength spectrometer measurement. The measurement’s precision, accuracy, reliability and reproducibility require professional, scrupulous and all-around attentions on analytical condition setting, which should be tested by multiple conditional analyses. Usually, to acquire optimal detection limit and low standard deviation, a simple approach is to set high initial energy (accelerate voltage, beam current) and long measurement time. In the meantime, at least other four major factors should also be paid attention to such as (1) analytical crystal selection in spectrometer, (2) characteristic X-ray spectrum interference and overlap identification and background value adjustment, (3) PHA function initiation and (4) standard material selection and standardization. In the last, we also need to answer the question about how many analyses data are required to ensure the validity and objectivity, i.e. the minimum measurement. It is suggested to apply iterative calculus from statistic mathematics in each measurement task, especially for studies with average content of trace elements in homogeneous samples.

    High Precision Analysis of Chemical Composition of SPI Monazite Standard on Large Spectrometer of 140 mm Rowland Circle
    HU Huan, WANG Rucheng, XIE Lei, ZHANG Wenlan, TIAN Enrong, XU Yating, FAN Hongrui
    2021, 27(3):  317-326.  DOI: 10.16108/j.issn1006-7493.2021036
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    Monazite is the bearing-LREE (light rare earth elements) phosphate mineral that occurs all types of rocks. It is an essential mineral for understanding the formation processes and U-Pb dating, thus high precision analysis of monazite chemical composition has an important geological significance, and also provides reliable parameters for follow-up studies, such as EMPA CHIME dating and in-situ isotopic microanalysis. EMPA is an in-situ and non-destructive technique with an excellent spatial resolution (~1 μm). Due to that, based on the detailed wavelength scanning for SPI Monazite standard, we focus on discussing the important issues in analytical procedure of monazite chemical composition: accelerate voltage, beam current, time, spectrometer, analysis lines, detected limits, interference factor and standards, and obtain the chemical composition data that are finely consistent with the recommended values of the SPI monazite standard under the optimal analysis conditions. This paper presents the best analytical set-up of JEOL JXA-8530F Plus electron microprobe facility at State key laboratory for mineral deposits research, Nanjing University, particularly establishes the high precision analysis of the trace rare earth elements on large spectrometer of 140 mm Rowland circle. The relative standard deviations (RSD) of all element contents are less than 20% (0.05%-17.75%)and meet the accuracy requirement of integration analysis of monazite composition and geochronology.

    Quantitative Analysis of Na by EPMA: Constraints for the Behavior of Na by the Crystal Structure
    ZHANG Wenlan , HU Huan, XIE Lei, WU Bin
    2021, 27(3):  327-339.  DOI: 10.16108/j.issn1006-7493.2021038
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    In the quantitative analysis of electron probe microanalysis, Na belongs to the unstable element (heating diffusion element), so it is difficult to measure accurately. Many works have been done on the problem, for example, quantitative analysis of Na-bearing glasses and Na-bearing minerals with different crystal structures by electron microprobe shows that the Na count decreased significantly with the extension of analysis time, and it is recognized that the decrease in the number of Na-bearing glasses is more obvious than that of Na-bearing minerals, showing that the decrease of Na count is related to the crystal structure of the sample,but the internal control factors are not clear. Based on previous studies, the typical Na-bearing minerals are studied with different structures: frame type, ring type, chain type, layered type and amorphous type (Na glass). By analyzing the position, coordination number, bond type and characteristics of Na atom in different crystal structures, as well as diffusion conditions of Na atoms in different crystal structures and additional accompanying anions, the internal reasons for the decrease of Na count were discussed, and the decreasing degree of Na count in different crystal structures was compared and analyzed. The descending order of Na counts of Na-bearing minerals with different crystal structures is as follows: noncrystalline>fram layered﹥circular﹥single chain﹥double chain, with additional anion﹥no accessory anion,and the Na-bearing minerals with additional anions are larger than those without accessory anions.Through the comparative analysis of Na count under different test conditions, it is found that the change of accelerating voltage, beam current and beam spot diameter will have a certain influence on Na counting. Combining the principle of Na count decrease of Na-bearing minerals with different crystal structures, the optimum analytical conditions for accurate determination of Na bearing silicate minerals are summarized, that provides a reference for the accurate determination of Na content in Na bearing minerals.

    EPMA Simultaneous Determination of An Element by Multi-spectrometer: A Case Study of the Determination of Al and Ti Contents in Quartz
    CUI Jiqiang, GUO Shengbin, ZHANG Ruoxi, XIE Jing, YANG Shuiyuan
    2021, 27(3):  340-348.  DOI: 10.16108/j.issn1006-7493.2021035
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    Electron probe microanalysis (EPMA) is a method for in-situ analysis of major element contents in minerals. However, it is a challenge to improve precision and accuracy for the analysis of trace elements by EPMA. Changing accelerating voltage, increasing beam current, and increasing counting time are the common methods to improve the precision. However, these methods are easy to destroy the samples and cause element migration, resulting in the inaccuracy of the analytical results. Increasing the counting time will also reduce the analytical efficiency. In this paper, a method of simultaneous determination of an element by multi-spectrometer is proposed to improve the intensity of characteristic X-ray. In this method, multi-spectrometer is used to measure the characteristic X-ray intensity of an element simultaneously. The total characteristic X-ray intensity of standard and unknow are obtained by multi-spectrometer. Then, combined the content of the element in the standard, the content of the element in unknows can be calculated. This method can significantly improve the characteristic

    X-ray intensity, leading to high precision and low detection limit. In this study, the contents of Al and Ti in a reference quartz standard were measured by the method of simultaneous determination of an element by multi-spectrometer, to verify the application of this method in trace element analysis. Two wavelength dispersive spectrometer with one TAP crystal and one TAPL crystal were used to measure Al simultaneously, and three wavelength dispersive spectrometer with three PETL crystals were used to measure Ti simultaneously. The multipoint background method, and the condition of 20 kV accelerating voltage, 500 nA beam current, and 20 μm beam diameter were used. The detection limit of Al and Ti in this study were 2.6×10-6(3σ) and 2.1×10-6(3σ), respectively. The analyses result of Al and Ti in this reference standard were
    163.8×10-6±5.8×10-6 (3σ) and 56.5×10-6±2.0×10-6 (3σ) respectively, which are all close to the reference values (154×10-6±15×10-6 for Al and 57×10-6±4×10-6 for Ti), and show a good long-term stability.

    The Time-dependent Drift Effect during ICP-MS Analysis
    DING Rui, ZHANG Yinggang, ZHU Zhiyong, LIN Zhengfan, YANG Tao
    2021, 27(3):  349-355.  DOI: 10.16108/j.issn1006-7493.2021039
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    The time-dependent drift is one of the main factors that control the data uncertainties in the analysis using inductively coupled plasma mass spectrometer. In this paper, a systematic study is carried out to explore the regularity and mechanism of the time-dependent drift effect of various elements. The results show that: (1) The degree of drift of various elements over time is significantly different; (2) The degree of drift is related to the mass of the studied element; (3) The distribution of different elements in the plasma are quite different, which may relate to the diffusion of elements in the plasma. In addition to the differences in the distribution patterns of the studied elements, the distribution patterns of elements in the plasma is unstable, and the combination of the two factors may lead to time-dependent drift. Finally, we found that the time-dependent drift is not affected by the concentration of elements. This research has important implication on understanding the time-dependent drift effect of inductively coupled plasma mass spectrometry and solutions to reduce the drift as well. 
    Application of Transmission Electron Microscopy in Microarea Analysis in Mineral
    CHEN Jiani
    2021, 27(3):  356-365.  DOI: 10.16108/j.issn1006-7493.2021037
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    Transmission electron microscope (TEM) is an important characterization method in nano-geology field which is a branch of modern earth science. TEM offers images with an ultra-high spatial resolution and diversified microanalysis methods. Because of the high complexity and strong heterogeneity of geological samples, the experimental process is complex and difficult when using TEM to analyze and study geological specimens. In this paper, aims to explore a scientific and appropriate testing scheme, the author pays attention to describe every test step. Firstly, according to the characteristics of samples, the appropriate sample preparation methods should be selected and the powder preparation method, ion thinning method and focused ion beam method are introduced. Then, the target minerals are searched, and a search method of SEM+TEM is proposed.Next, different kinds of images are acquired, including bright field image, dark field image, high resolution image, electron diffraction pattern and so on, each theory, process, notices and experimental skills are related and analyzed in detail. Finally, the micro area concerned is selected to test the elements composition and distribution, and commonly used micro area elements composition analysis instruments are compared to illustrate the advantages and the scope of TEM elements analysis.
    Detrital Feldspars of the Chinese Deserts: Implications for Asian Dust Provenance
    LI Juan, HE Tong
    2021, 27(3):  366-374.  DOI: 10.16108/j.issn1006-7493.2020067
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    Using an automated mineral identification technique (INCA-Mineral), we quantified the mineral compositions for the sediments that are collected from ten desert basins in East Asia. The mineralogical characteristics of felsic minerals were analyzed to determine the variation in spatial scale. Using the felsic component, e.g. quartz-plagioclase-K-feldspar compositions, results demonstrate that the desert basin along the Central Asian Orogenic Belt possess higher K-feldspar/albite ratios and higher Ca-plagioclase/quartz ratios, compared with that of the desert basins along northern Tibetan Plateau. The two end-member classification of desert sediments in East Asia was supported by previous studies using Nd-Sr-Hf isotopic fingerprinting method. The felsic mineralogical characteristic parameter showed similarity between the dust source deserts from the SDB and the glacial dusts on the Loess Plateau. These results strongly indicate that the northern Tibetan Plateau was the dominant dust material source for Chinese loess. Combined with the previous study by method of air mass back trajectory and geomorphology, the dust material contributions from the Central Asian Orogenic Belt was also potentially included via the long-distance wind transport.