电子探针-电感耦合等离子体质谱法研究不同种类石榴石的稀土元素配分和矿物学特征

贾玉衡; 钱建平

doi:10.15898/j.cnki.11-2131/td.202005060007

电子探针-电感耦合等离子体质谱法研究不同种类石榴石的稀土元素配分和矿物学特征

贾玉衡,
钱建平^,

桂林理工大学地球科学学院, 广西桂林 541006

基金项目:
中国地质科学院地质研究所基本科研业务费项目（J2004）；自然资源部中国地质调查局勘测计划（DD201900660，DD20190629）

详细信息

作者简介: 贾玉衡, 博士研究生, 地质资源与地质工程专业。E-mail:yuhengjia@glut.edu.cn

通讯作者: 钱建平, 博士生导师, 主要从事矿床和地球化学研究。E-mail:jpjian@163.com

中图分类号: P574;O657.63

收稿日期: 2020-04-15

修回日期: 2020-08-06

录用日期: 2020-09-19

Study on REE Distribution and Mineralogical Characteristics of Different Garnets by Electron Probe and Inductively Coupled Plasma-Mass Spectrometry

Yu-heng JIA,
Jian-ping QIAN^,

College of Earth Sciences, Guilin University of Technology, Guilin 541006, China

More Information

Corresponding author: Jian-ping QIAN, jpjian@163.com

Received Date: 15 April 2020

Revised Date: 06 August 2020

Accepted Date: 19 September 2020

摘要

摘要: 石榴子石是变质岩和岩浆岩中一种常见的硅酸盐矿物，其类质同象非常普遍。已有资料表明，不同成分的石榴子石的颜色颇为不同，但石榴子石的成分和颜色之间相互关系尚未进行系统研究和总结。本文应用电子探针、电感耦合等离子体质谱、X射线粉晶衍射、拉曼光谱、红外光谱和紫外可见吸收光谱等手段对常见的红色（G1）、橙色（G2）、绿色（G3）和褐红色（G4）石榴石进行了系统测试，旨在揭示石榴子石成分、结构和颜色的内在关系和变异规律，以期为不同地质体中产出的石榴子石矿物学特征的总结及地质应用提供依据。研究结果表明，G1、G4样品含有较多Fe元素（Fe³⁺：0.24%、0.24%；Fe²⁺：1.01%、0.89%）；G2样品含有较高的Mn元素（2.76%）；G3样品含有很高的Cr、V元素（3453×10^-6、1458×10^-6）。类质同象对石榴石的晶体结构产生影响，晶胞参数有较大差别，分别是a=11.530nm（G1）、11.563nm（G2）、11.849nm（G3）和11.470nm（G4）。石榴石中的微量元素和稀土元素对于示踪物源及形成过程具有很强的指示意义。石榴石中的稀土元素总量分布不均匀，LREE/HREE比值小于1，表现为重稀土元素富集，Eu/Eu^*比值小于1，为Eu负异常。所有样品的Ce异常均不明显。石榴石样品的拉曼光谱呈现出峰强和峰位的明显差异也反映了类质同象的存在：G1、G4在570nm处出现Fe³⁺电子跃迁吸收峰；G2在460nm和520nm附近出现Mn²⁺电子跃迁吸收峰；G3在690nm处出现Cr³⁺电子跃迁吸收峰。紫外可见吸收光谱特征显示，红色和褐红色样品出现在570nm处的Fe³⁺电子跃迁吸收峰，与其成分中含有大量Fe有关；橙色样品于460nm和520nm附近的特征吸收峰归属于Mn²⁺，对应其主要成分中大量的Mn；绿色样品690nm处出现强的吸收峰，由Cr³⁺跃迁产生，是微量元素Cr的存在所致。研究结果表明，石榴石的颜色与其成分和结构具有良好的对应关系。
- 石榴石 /
- 类质同象替换 /
- 稀土元素配分 /
- 矿物学特征
Abstract: BACKGROUNDGarnet is a common silicate mineral in metamorphic and magmatic rocks, and its isomorphism is very common. The existing data show that the color of garnet with different composition is quite different, but the relationship between the composition and color of garnet has not been systematically studied. OBJECTIVESTo reveal the internal relationship and variation law of garnet composition, structure and color, and provide a basis for the summary and geological application of the mineralogical characteristics of garnet in different geological environments. METHODSCommon red (G1), orange (G2), green (G3) and maroon (G4) garnet have been tested systematically by electron microprobe, inductively coupled plasma-mass spectrometry, X-ray powder crystal diffraction, Raman spectroscopy, infrared spectroscopy and ultraviolet-visible absorption spectroscopy. RESULTSThe results showed that the samples of G1 and G4 contained more Fe (Fe³⁺:0.24%, 0.24%, Fe²⁺:1.01%, 0.89%). The samples of G2 contained higher Mn (2.76%), whereas the samples of G3 have higher Cr and V contents of 3453×10^-6 and 1458×10^-6, respectively. Isomorphic substitution greatly affected the crystal structure of garnet. The cell parameters were a=11.530nm(G1), 11.563nm(G2), 11.849nm(G3) and 11.470nm(G4). Trace and rare earth elements in garnet can be used to indicate the source and formation process. The rare earth element analysis showed that the total rare earth elements of garnet were distributed unevenly, and the ratio of LREE/HREE was less than 1, with enriched heavy rare earth elements. The Eu/Eu^* ratio was less than 1, which was a negative Eu anomaly. Ce abnormalities of all samples were not obvious. G1 and G4 have Fe³⁺ electronic transition absorption peak at 570nm. G2 has Mn²⁺ electronic transition absorption peak near 460nm and 520nm, whereas G3 has Cr³⁺ electronic transition absorption peaks at 690nm. The Raman spectra of garnet samples showed obvious differences in peak intensity and position, which also reflected the ubiquitous existence of isomorphism in these garnets. The ultraviolet-visible absorption spectra of these garnets showed high consistency with its color and characteristic elements. The absorption peaks of Fe³⁺ in red and maroon samples at 570nm were related to the high content of Fe, while the characteristic absorption peaks of orange sample near 460 and 520nm belong to Mn²⁺, corresponding to the large amount of Mn (2.76%). A strong absorption peak was observed at 690nm in the green sample, which was caused by the transition of Cr³⁺ and the presence of trace element Cr (3453×10^-6). The results showed that the color of garnet had a good correspondence with its composition and structure. CONCLUSIONSThe color characteristics of garnet can be used as a typomorphic feature of minerals to indicate the existence of different characteristic elements. These methods can be used to study the isomorphism and color origin of garnet effectively.
- garnet /
- isomorphic replacement /
- distribution of rare earth elements /
- mineralogy characteristics

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图 1 石榴石样品稀土元素配分曲线

Figure 1.

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图 2 石榴石样品X射线粉晶衍射谱图

Figure 2.

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图 3 石榴石样品红外光谱

Figure 3.

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图 4 石榴石样品拉曼光谱

Figure 4.

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图 5 石榴石样品紫外可见吸收光谱

Figure 5.

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表 1 石榴子石样品中的主量元素电子探针分析结果

Table 1. EMPA results of major elements in garnet samples

样品编号	含量(%)
样品编号	SiO₂	TiO₂	Al₂O₃	Cr₂O₃	FeO	MnO	MgO	CaO	8种氧化物之和	Si	Ti	Al	Cr	Fe³⁺	Fe²⁺	Mn	Mg	Ca	Uvt	And	Py	Sps	Grs	Alm
G1	37.65	0	21.34	0	19.87	4.12	16.13	1.33	100.44	2.82	0	1.88	0	0.24	1.01	0.26	1.8	0.11	0	11.1	56.66	8.22	0	31.76
G2	35.67	0.06	19.99	0	0.84	39.39	2.23	0.75	98.93	2.95	0	1.95	0	0.06	0	2.76	0.28	0.07	0	2.81	8.87	88.99	0	0
G3	36.60	0.40	20.74	0.17	0.06	5.98	0.55	34.81	99.31	2.85	0.02	1.91	0.01	0	0	0.40	0.06	2.91	0.47	0.17	1.9	11.37	85.73	0
G4	37.61	0.06	21.34	0	18.03	4.52	15.87	3.04	100.47	2.81	0	1.88	0	0.24	0.89	0.29	1.77	0.24	0	11.41	55.56	8.99	0	27.8
注：以12个氧原子和8个阳离子为计算基础。Uvt—钙铬榴石; And—红柱石; Py—黄铁矿; Sps—锰铝榴石; Grs—钙铝榴石。

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表 2 石榴石样品中的微量元素和稀土元素组成

Table 2. Trace elements and rare earth elements composition of garnet samples

微量元素	含量(×10^-6)
微量元素	G1	G2	G3	G4
Cr	233	60.9	3453	126
V	132	1.42	1358	30.3
Zn	3447	1851	2188	3116
Ni	1.21	2.09	< 0.05	3.3
Rb	0.18	0.38	0.25	0.21
Sr	3.60	1.93	3.83	1.59
Ba	4.31	6.39	3.55	1.66
Pb	2.92	0.85	1.68	0.84
Nb	12.6	19.8	13.8	1.43
Ta	0.31	0.35	0.15	0.32
Zr	18.7	10.3	43.9	88.9
Hf	1.21	1.01	2.1	2.55
Be	< 0.05	0.59	1.03	0.07
Sc	282	5.67	11.8	118
Cu	2.49	4.25	2.22	2.18
Ga	7.93	51.7	77.8	5.51
Mo	0.42	0.13	0.52	0.29
Cd	0.90	0.56	0.18	0.24
Cs	0.05	0.16	0.2	0.06
W	1.02	0.45	0.39	0.85
La	0.39	0.42	0.2	6.58
Ce	0.26	0.85	0.2	7.07
Pr	41.5	1.23	4.9	101
Nd	1.03	0.63	0.9	8.93
Sm	12.7	7.59	5.9	32.6
Eu	4.76	21.9	12	47.8
Gd	52.9	52.5	18	108
Tb	123	130	26	187
Dy	181	171	30	232
Ho	191	169	28	235
Er	205	181	32	269
Tm	196	175	33	271
Yb	189	169	36	269
Lu	174	161	36	243
Y	202	190	33	276
REE	1574	1433	296	2293
LREE/ HREE	0.04	0.02	0.1	0.1
Eu/Eu^*	0.15	0.73	1	0.68
Ce/Ce^*	0.01	1.04	0.1	0.13
注：Eu/Eu^=2Eu_N/(Sm_N+Gd_N)，无单位；Ce/Ce^=2Ce_N/(La_N+Pr_N)，无单位；LREE/HREE无单位。

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