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庞江,张烨毓,黄毅,等. 铁含量对白云石拉曼光谱特征的影响[J]. 岩矿测试,2023,42(4):852−862. DOI: 10.15898/j.ykcs.202211030210
引用本文: 庞江,张烨毓,黄毅,等. 铁含量对白云石拉曼光谱特征的影响[J]. 岩矿测试,2023,42(4):852−862. DOI: 10.15898/j.ykcs.202211030210
PANG Jiang,ZHANG Yeyu,HUANG Yi,et al. Effect of Fe Content on Raman Spectral Characteristics of Dolomite[J]. Rock and Mineral Analysis,2023,42(4):852−862. DOI: 10.15898/j.ykcs.202211030210
Citation: PANG Jiang,ZHANG Yeyu,HUANG Yi,et al. Effect of Fe Content on Raman Spectral Characteristics of Dolomite[J]. Rock and Mineral Analysis,2023,42(4):852−862. DOI: 10.15898/j.ykcs.202211030210

铁含量对白云石拉曼光谱特征的影响

Effect of Fe Content on Raman Spectral Characteristics of Dolomite

  • 摘要: 白云石中Fe含量分析是研究白云石(岩)成因的重要手段,研究白云石中Fe含量与拉曼光谱之间的关系能够提供一种利用拉曼光谱原位测定白云石中Fe含量的潜在方法。本次研究应用显微共聚焦激光拉曼光谱仪对不同Fe含量的白云石进行了拉曼光谱分析,并对其拉曼光谱变化特征进行了研究。研究结果表明,相较于白云石,铁白云石各个拉曼特征峰均向低频方向偏移。白云石的拉曼特征峰位移与Fe含量呈明显的线性关系,随着Fe含量增加,白云石的各个拉曼特征峰位移均减小。相较于CO32−基团内部振动特征峰(v1v3v4峰),两个晶格振动特征峰(T峰和L峰)随Fe含量变化的偏移更为明显。研究认为,由于Fe2+的离子半径大于Mg2+,当Fe2+替代白云石晶格中的Mg2+后,晶格中金属-氧键平均键长变长、平均键能变弱,从而改变了金属-氧键和C-O键拉曼活性振动,致使拉曼特征峰向低频方向偏移。本次研究初步建立了基于拉曼光谱中L峰和v1峰的峰间距测定白云石中Fe含量的方法,与传统方法相比,该方法对样品要求较低,能够进行非破坏性测试。

     

    Abstract:
    BACKGROUND Dolomite is a common carbonate mineral in sedimentary rocks, and dolomite rock serves as an important reservoir rock for oil and gas. However, the production of synthetic dolomite under normal temperature and pressure is not yet possible, the genesis of dolomite and dolomite reservoirs has been a difficult problem to understand in geological research. Fe ion is a prevalent impurity element in natural dolomite, and the Fe content in dolomite can serve as an indicator of the diagenetic environment, which provides valuable insights into the genesis of dolomite. The technology of Raman spectroscopy has evolved from qualitative analysis to quantitative analysis. Therefore, the quantitative characterization of carbonate mineral chemical composition can be accomplished using Raman spectroscopy. Previous studies have shown that the Raman spectra of calcite group minerals shift regularly with the change of cation composition. However, there is no systematic study on the relationship between Fe content and Raman spectrum in dolomite.
    OBJECTIVES To discuss the influence of Fe content on the Raman spectrum of dolomite, and establish a test method for the determination of Fe content in dolomite by Raman spectroscopy.
    METHODS Seven dolomite samples from the Maokou Formation were collected from a well in the Sichuan Basin. Based on the petrography observation under a microscope, different types of dolomite with relatively clean grains were selected for EPMA to obtain the chemical composition of dolomite, then microscopic confocal laser Raman spectroscopy was conducted in the same area to acquire the corresponding dolomite Raman spectra. In addition, Raman spectra and corresponding chemical composition data of 14 typical dolomite samples were obtained from the RRUFF database for this study. The effect of Fe content on Raman spectroscopy of dolomite was studied by analyzing the correlation between the characteristic parameters of dolomite Raman spectroscopy and Fe content.
    RESULTS (1) Raman peaks for two lattice vibration (T and L) and three CO32− group internal vibration (v1, v3 and v4) were observed in the dolomite Raman spectrum. Compared with dolomite, each Raman peak position of ankerite moves to a lower frequency. Moreover, the Raman shifts of T and L peaks of ankerite are reduced by 5cm−1 and 13cm−1 on average, and the Raman shifts of v1, v3 and v4 peaks are reduced by 3cm−1, 2cm−1 and 2cm−1 on average, respectively.  (2) There is an obvious linear relationship between the Raman shift and their Fe content of dolomite minerals. The measured Raman shift decreases with the increase of Fe content in dolomite. Notably, the movement of the peak position of the lattice vibration mode is more obvious, with the change of Fe content in dolomite, compared with the internal vibration peak.  (3) Because the ionic radius of Fe2+ is larger than that of Mg2+, when Fe2+ replaced Mg2+ in the dolomite lattice, the average length of the metal-oxygen bond in minerals becomes longer, and the bond energy becomes weaker. Thus, with the changing of the Raman active vibration mode, Raman shifts of each peak in the dolomite Raman spectrum decreases.
    CONCLUSIONS Based on the different influences of Fe content in dolomite on the Raman shift of lattice vibration peaks and internal vibration peaks in Raman spectroscopy, a testing method for determining Fe content in dolomite is preliminarily established based on the distance between L peak and v1 peak in Raman spectroscopy. Compared with traditional methods for testing the Fe content in dolomite, this method has lower requirements for samples and can be used for non-destructive testing, and is suitable for artificial synthesis experiments of dolomite.

     

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