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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[CO3]2−基团内部振动特征峰（v1、v3和v4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。
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关键词:
- 白云石 /
- 显微共聚焦激光拉曼光谱 /
- 电子探针 /
- 拉曼位移 /
- Fe含量
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 [CO3]2− 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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图 2 不同成分白云石的拉曼光谱特征（KY-1、KY-2、KY-2-2、KY-3、KY-4、KY-5、KY-5-2、KY-6、KY-6-2和KY-7号红色谱图为本次研究获得，其余黑色谱图收集自RRUFF数据库）
Figure 2.
表 1 白云石矿物拉曼特征峰位移及化学成分数据
Table 1. Dates of Raman peak position and chemical composition of dolomite minerals.
样品编号 矿物种类 化学成分（%） 拉曼特征峰峰位（cm−1） 数据来源 MgO CaO MnO FeO T L L2 v4 v2 v1 v3 KY-1 白云石 20.60 32.40 0.02 0.08 177 301 / 724 / 1098 1445 本次研究 KY-2 白云石 21.90 30.45 / / 176 300 / 726 / 1098 1441 KY-2-1 白云石 18.74 27.21 0.10 5.88 173 296 / 722 / 1095 1440 KY-3 白云石 21.97 30.85 / 0.04 176 301 / 724 / 1097 1445 KY-4 白云石 21.84 30.85 / 0.03 176 300 / 725 / 1098 1441 KY-5 白云石 21.81 29.95 0.01 0.04 177 299 / 725 / 1097 1443 KY-5-1 白云石 16.02 27.55 0.37 9.14 171 293 / 722 / 1094 1438 KY-6 白云石 18.01 28.74 0.01 6.32 172 293 / 723 / 1094 1440 KY-6-2 白云石 21.79 30.63 / 0.04 175 297 / 723 / 1095 1442 KY-7 白云石 19.78 29.07 0.01 4.17 173 294 / 723 / 1095 1443 R050181 铁白云石 6.87 27.16 1.69 20.57 170 284 / 723 / 1094 1443 RRUFF数据库
（http://rruff.info/ ）R050197 铁白云石 6.88 29.87 1.60 17.95 170 284 / 720 / 1093 1436 X050018 铁白云石 - - - - / 283 / 724 / 1092 1438 X050019 铁白云石 - - - - / 288 / 724 / 1095 1441 R040030 白云石 21.32 29.75 0.09 0.00 178 302 341 726 883 1100 1444 R050129 白云石 13.22 29.68 1.07 10.84 171 290 / 721 / 1092 1437 X050062 白云石 - - - - / 302 / 726 883 1097 / X050063 白云石 - - - - / 302 / 726 881 1097 / R050241 白云石 20.71 26.88 0.08 0.62 176 299 339 725 881 1098 1442 R050272 白云石 12.60 27.60 7.48 6.84 173 295 / 722 / 1095 1441 R050357 白云石 18.37 29.06 0.12 0.65 176 300 338 725 882 1098 1442 R050370 白云石 16.36 26.53 0.70 6.40 172 291 / 723 / 1094 1440 R100118 白云石 - - - - 178 301 340 726 882 1099 / R100168 白云石 - - - - 177 301 340 725 882 1099 / 注：“-”表示未进行测试，“/”表示未检出或低于检测限。 
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表 2 方解石、白云石和菱铁矿拉曼活性振动特征峰峰位（据文献[29，31]修改）
Table 2. Summary of Raman peak positions for lattice vibration and internal vibration modes in calcite, dolomite, magnesite （Modified from Reference [29,31]）.
拉曼活性振动模式 峰位（cm−1） 方解石 白云石 菱镁矿 晶格振动 T（平移） 154 175 213 L（摆动） 284 299，331 329 内部C—O键
振动v1（对称伸缩） 1085 1097 1094 2v2（面外弯曲） 1748 1750 1762 v3（反对称伸缩） 1434 1439 1444 v4（面内弯曲） 711 724 738
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