安徽泾县湛岭斑岩型钼矿床中铼的赋存状态研究

陈雪锋; 范裕; 周涛发

doi:10.18654/1000-0569/2021.09.07

安徽泾县湛岭斑岩型钼矿床中铼的赋存状态研究

- 1.
  合肥工业大学资源与环境工程学院, 合肥工业大学矿床成因与勘查技术研究中心(ODEC), 合肥 230009
- 2.
  安徽省矿产资源与矿山环境工程技术研究中心, 合肥 230009
基金项目:
本文受国家自然科学基金项目（41872081、91962218）和中央高校基本科研业务费专项（PA2019GDZC0093）联合资助

详细信息

作者简介:
陈雪锋, 男, 1989年生, 博士, 地质学专业, E-mail: xfchen2016@126.com

通讯作者: 范裕, 男, 1982年生, 教授, 博士生导师, 矿物学、岩石学、矿床学专业, E-mail: fanyu@hfut.edu.cn

中图分类号: P618.65;P618.87

收稿日期: 2021-06-02

修回日期: 2021-08-21

刊出日期: 2021-09-01

The occurrence of rhenium in the Zhanling porphyry molybdenum deposit, Jing County, Anhui Province

- 1.
  School of Resources and Environmental Engineering, Ore deposit and exploration Centre(ODEC), Hefei University of Technology, Hefei 230009, China
- 2.
  Anhui Province Engineering Research Center for Mineral Resources and Mine Environments, Hefei 230009, China

More Information

Corresponding author: FAN Yu, E-mail: fanyu@hfut.edu.cn

Received Date: 02 June 2021

Revised Date: 21 August 2021

Publish Date: 01 September 2021

摘要

摘要:
铼（Re）作为关键金属之一，是国家安全和军事战略必不可少的关键矿产，近年来受到世界各国的广泛关注。目前全球90%的Re产出于斑岩型矿床中，由于Re和Mo（钼）的元素性质相近，辉钼矿是Re的主要富集矿物。目前，前人的研究主要集中于含Re辉钼矿多型、辉钼矿中Re的含量、以及微米尺度上Re在辉钼矿中的赋存规律等方面，但纳米尺度上，Re在辉钼矿中的赋存状态研究仍十分薄弱。本次工作以安徽省泾县新发现的湛岭斑岩型钼矿床中的辉钼矿为研究对象，查明矿床中的辉钼矿主要有两种类型：粗粒叶片状辉钼矿（Ⅰ型）和细粒集合体辉钼矿（Ⅱ型）。通过电子探针（EPMA）和激光剥蚀电感耦合等离子质谱仪（LA-ICP-MS）确定了微米尺度上辉钼矿中的Re含量呈较大的不均一性。粗粒叶片状辉钼矿核部的Re含量（90.2×10^-6）高于边部（37.6×10^-6），细粒集合体辉钼矿中的Re平均含量（89.4×10^-6）明显高于粗粒叶片状辉钼矿（50.0×10^-6），其中可见多个无规律的局部Re富集区域。在此基础上，对细粒集合体辉钼矿中富Re区域进行聚焦离子束（FIB）原位取样，并运用透射电镜（TEM）分析发现，在纳米尺度上，辉钼矿Re含量也有较大不均一性。在ADF-TEM照片中识别出辉钼矿具有a、b两种不同的表征。表征a的辉钼矿Re含量较高，晶格受到明显干扰，除类质同象替换外，还存在以Re-S吸附的方式赋存的Re；而表征b中的辉钼矿Re含量较低，晶格并未受到明显的干扰，Re主要是以类质同象替换的形式存在。以上研究结果表明，湛岭斑岩型钼矿床中的Re除了类质同象替代Mo进入辉钼矿晶格外，还以Re-S的形式吸附在辉钼矿晶格表面，Re的两种赋存状态是辉钼矿中Re含量不均一性的主要原因。
- 铼 /
- 赋存状态 /
- 透射电镜 /
- 湛岭斑岩型钼矿床
Abstract:
Rhenium (Re) as one of the significant critical metals and essential for national security and military strategies. It has attracted extensive attention in recent years. At present, 90% of Re resources was produced in porphyry deposits in the world. Re is mainly enriched in molybdenite, due to the similar element properties of Re and Mo (molybdenum). However, the nanoscale occurrence and enrichment mechanisms of Re in molybdenite is still need to be further studied. This work focuses on the molybdenite in the newly discovered Zhanling porphyry molybdenum deposit in the Jiangnan uplift belt. The molybdenite is the main rhenium-bearing mineral with two types, such as coarse-grained leaf-shaped molybdenite (Type-Ⅰ) and fine-grained aggregate molybdenite (Type-Ⅱ) which is slightly later. LA-ICP-MS trace element analysis results showed that the Re average contents in the Type-Ⅱ (89.4×10^-6) is significantly higher than that Type-Ⅰ (50.0×10^-6), but the Re shows obvious irregular enrichment in the individual grain of Type-Ⅰ. Generally, the contents of Re is higher in the core (89.4×10^-6), but lower in the edge (37.6×10^-6). Through TEM observation on the Re-rich regions in the Type-Ⅱ, two different characteristics of molybdenite has been recognized in the ADF-TEM photos. The characterization a of molybdenite has a relatively high Re contents. Besides isomorphic substitution in the lattice of molybdenite, Re atoms also occur as Re-S adsorption form exist in molybdenite. While the characterization b of molybdenite shows a relatively lower Re contents and Re mainly exists in the form of isomorphic substitution. Therefore, we emphasize that most of Re substituted Mo in the molybdenite crystal lattice, and few Re can be adsorbed on the surface of the molybdenite crystal as the Re-S form, which resulting the Re microheterogeneity in molybdenite.
- Rhenium /
- Occurrence /
- TEM /
- Zhanling porphyry molybdenum deposit

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图 1

湛岭钼矿床区域地质图(据江西省地质矿产局, 1984修改)

Figure 1.

Geological map of the Zhanling molybdenum deposit (modified after BGMRJ, 1984)

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图 2

湛岭钼矿床矿区地质略图(据安徽同跃矿业有限公司, 2011)

Figure 2.

Geological map of the Zhanling molybdenum deposit

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图 3

湛岭钼矿床辉钼矿矿石手标本和反射光镜下照片

Figure 3.

Hand specimens and microstructural features of the molybdenite from the Zhanling molybdenum deposit

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图 4

湛岭钼矿床中辉钼矿(样品12-204)面扫描微量元素分布图

Figure 4.

The trace element mapping of molybdenite (Sample 12-204) from Zhanling molybdenum deposit

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图 5

湛岭钼矿床中辉钼矿(样品12-407)面扫描微量元素分布图

Figure 5.

The trace element mapping of molybdenite (Sample 12-407) from Zhanling molybdenum deposit

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图 6

湛岭钼矿床中辉钼矿(样品12-576)的微量元素分布图

Figure 6.

The trace element mapping of molybdenite (Sample 12-576) from Zhanling molybdenum deposit

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图 7

湛岭钼矿床辉钼矿FIB取样位置及HAADF-EDS面扫描图

Figure 7.

The FIB location and HAADF-EDS mapping of the molybdenite in Zhanling molybdenum deposit

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图 8

湛岭钼矿床中辉钼矿不同区域对应的Re元素波峰图及原子分数值

Figure 8.

Peak value and atomic faction of rhenium in different area of molybdenite in the Zhanling molybdenum deposit

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图 9

湛岭钼矿床辉钼矿样品中呈带状表征(表征a)的辉钼矿TEM高分辨率图

Figure 9.

High resolution TEM image of the belt molybdenite in Zhanling molybdenum deposit

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图 10

湛岭钼矿床呈面状表征(表征b)的辉钼矿TEM高分辨率图

Figure 10.

High resolution TEM image of the planar molybdenite in Zhanling molybdenum deposit

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图 11

湛岭钼矿床中辉钼矿多型XRD谱图

Figure 11.

The XRD spectral diagrams of the molybdenite from Zhanling molybdenum deposit

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图 12

湛岭钼矿床辉钼矿中Mo与Ag、Fe、Mn、Pb、Re、W、V、Ti、Cu的相互关系图解

Figure 12.

Diagrams of the relationship between Mo and Ag, Fe, Mn, Pb, re, W, V, Ti and Cu in molybdenite of Zhanling molybdenum deposit

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图 13

2H型辉钼矿中Re原子在辉钼矿中的赋存方式(据Lin et al., 2014)

Figure 13.

Occurrence mode of rhenium atoms in 2H-type molybdenite (after Lin et al., 2014)

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图 14

湛岭钼矿床辉钼矿中表征a(a、c)和表征b(b、d)的Re原子替换模型

Figure 14.

Occurrence mode of rhenium atoms in the characteristic a (a, c) and b (b, d) in the molybdenite from the Zhanling molybdenum deposit

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表 1

湛岭钼矿床中辉钼矿电子探针成分(wt%)数据表

Table 1.

Representative EPMA of chemical composition (wt%) of molybdenite from the Zhanling molybdenum deposit

测点号	Mo	S	As	Cr	Fe	Mn	Ni	W	Zn	Cu	Total
12-204-1(Ⅰ型)	59.42	40.15	Bdl	0.15	Bdl	Bdl	0.02	0.09	Bdl	0.07	99.89
12-204-2(Ⅰ型)	59.54	40.15	Bdl	0.19	Bdl	Bdl	Bdl	0.03	0.10	Bdl	100.0
12-204-3(Ⅰ型)	59.15	40.49	0.02	0.09	Bdl	0.01	Bdl	Bdl	0.04	0.02	99.80
12-204-4(Ⅱ型)	59.18	40.47	Bdl	0.13	0.08	Bdl	Bdl	0.02	Bdl	Bdl	99.88
12-204-5(Ⅱ型)	59.09	40.23	Bdl	0.19	0.14	Bdl	0.01	0.11	Bdl	0.05	99.81
12-407-1(Ⅱ型)	59.53	40.10	Bdl	0.23	0.00	Bdl	Bdl	Bdl	Bdl	Bdl	99.86
12-407-3(Ⅱ型)	59.29	40.57	Bdl	Bdl	0.03	Bdl	0.01	Bdl	0.07	Bdl	99.97
12-407-4(Ⅱ型)	58.99	40.84	Bdl	0.01	0.01	Bdl	Bdl	0.03	0.03	0.06	99.96
12-407-5(Ⅰ型)	59.92	39.65	Bdl	0.15	Bdl	Bdl	Bdl	Bdl	0.09	0.11	99.93
12-576-1(Ⅰ型)	59.55	40.03	Bdl	0.10	0.02	Bdl	Bdl	0.09	Bdl	0.12	99.92
12-576-2(Ⅰ型)	60.01	39.85	Bdl	Bdl	0.04	Bdl	Bdl	Bdl	0.02	0.02	99.95
12-576-4(Ⅱ型)	60.23	39.60	Bdl	0.04	0.02	0.01	0.01	0.03	Bdl	0.01	99.96
12-576-5(Ⅰ型)	59.07	40.80	0.02	0.00	0.03	Bdl	0.03	Bdl	Bdl	0.04	99.96
注：Bdl为低于0.01检测限

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表 2

湛岭钼矿床中辉钼矿微量元素(×10^-6)数据表

Table 2.

Trace element compositions (×10^-6) of molybdenite analyzed by LA-ICP-MS from Zhanling molybdenum deposit

测点号	Sc	Ti	V	Cr	Mn	Co	Ni	Zn	As	Ag	Cd	Sn	W	Re	Au	Pb
12-204-1(Ⅰ型)	0.00	11.1	6.04	4.92	0.00	0.04	1.93	0.00	3.83	1.06	6.37	0.00	21.3	43.2	0.11	23.7
12-204-2(Ⅰ型)	0.15	11.5	3.24	4.18	0.00	0.00	2.13	0.09	0.14	1.67	6.42	0.03	15.4	54.3	0.01	18.1
12-204-3(Ⅰ型)	0.00	18.0	3.06	0.00	0.00	0.02	0.00	1.44	1.17	0.00	7.58	0.00	14.6	90.2	0.27	35.2
12-204-4(Ⅱ型)	0.00	4.86	3.34	46.3	0.00	1.70	0.73	0.39	0.73	2.67	4.21	0.00	16.6	204	0.00	35.1
12-407-1(Ⅱ型)	0.00	0.00	8.21	367	0.00	77.7	23.2	271	16.7	1.11	0.00	4.55	32.1	37.6	0.00	16.2
12-407-3(Ⅱ型)	0.03	19.0	18.6	45.1	0.00	21.1	2.34	3.45	1.70	2.03	7.23	0.00	38.8	56.2	0.00	23.5
12-407-4(Ⅱ型)	1.75	11.0	36.3	8.23	11.3	34.8	2.45	62.9	3.50	1.45	6.70	0.20	38.7	61.4	0.18	15.1
12-407-5(Ⅰ型)	1.99	18.1	65.6	472	8.95	22.4	2.68	27.2	3.67	1.78	6.79	0.57	29.7	26.1	0.02	17.2
12-576-1(Ⅰ型)	0.03	19.0	14.7	10.2	0.31	0.63	0.00	3.75	0.14	4.49	8.74	0.19	27.2	38.0	0.00	28.1
12-576-2(Ⅰ型)	0.02	9.80	16.7	18.4	4.28	0.78	0.67	7.17	2.17	1.17	6.56	0.00	45.5	49.0	0.18	16.3
12-576-4(Ⅱ型)	0.00	17.1	8.41	2.65	2.86	2.31	0.00	6.70	33.0	15.7	5.37	0.00	30.9	87.6	0.63	20.1

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表 3

湛岭钼矿床辉钼矿不同区域对应的元素原子分数统计表

Table 3.

Atomic faction of rhenium in different area of molybdenite in Zhanling molybdenum deposit

元素	原子分数(%)	误差(%)	元素	原子分数(%)	误差(%)
Area#1			Area#3
S	39.7	7.38	S	58.9	8.72
Fe	0.39	0.1	Fe	0.3	0.07
Mo	58.4	13.9	Mo	39.8	8.33
W	0.43	0.1	W	0.31	0.06
Re	0.48	0.11	Re	0.29	0.06
Pb	0.62	0.14	Pb	0.43	0.08
Area#2			Area#4
S	60	8.67	S	35.3	6.85
Fe	0.25	0.06	Fe	0.51	0.13
Mo	38.7	8.03	Mo	62.8	15.3
W	0.29	0.06	W	0.35	0.08
Re	0.27	0.05	Re	0.41	0.09
Pb	0.45	0.09	Pb	0.62	0.14

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