川南兴文地区上二叠统龙潭组下部黏土岩中铌的富集特征及赋存状态

周颂德; 梁斌; 郝雪峰; 唐屹; 何洋飘; 潘蒙; 张彤; 付小方

doi:10.19509/j.cnki.dzkq.tb20230682

川南兴文地区上二叠统龙潭组下部黏土岩中铌的富集特征及赋存状态

doi: 10.19509/j.cnki.dzkq.tb20230682

周颂德^{1, 2,},
梁斌^{1, 2, ,},
郝雪峰²,
唐屹²,
何洋飘³,
潘蒙²,
张彤²,
付小方²

1 .
西南科技大学环境与资源学院，四川绵阳 621000
2 .
四川省综合地质调查研究所，成都 610081
3 .
四川省第七地质大队，四川乐山 614000

基金项目: 四川省地质调查研究院重大专项（SCIGS-CZDXM-2023002）；四川省自然科学基金项目（23NSFSC0191）；国家重点研发计划项目（2017YFC0602702）

详细信息

作者简介:
周颂德：E-mail：731484533@qq.com

通讯作者:
E-mail：earlliuh@163.com

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- 文章访问数: 98
- PDF下载量: 3
- 被引次数: 0
出版历程
- 收稿日期: 2023-12-08
- 录用日期: 2024-04-19
- 修回日期: 2024-04-16
- 网络出版日期: 2025-04-17

Enrichment characteristics and occurrence of Nb in clay rocks in the lower part of Upper Permian Longtan Formation in Xingwen area, Southern Sichuan

ZHOU Songde^{1, 2
,},
LIANG Bin^{1, 2
, ,},
HAO Xuefeng²,
TANG Yi²,
HE Yangpiao³,
PAN Meng²,
ZHANG Tong²,
FU Xiaofang²

1 .
School of Environment and Resources, Southwest University of Science and Technology, Mianyang Sichuan 621000, China
2 .
Sichuan Institute of Geological Survey, Chengdu 610081, China
3 .
The 7th Geological Brigade of Sichuan, Leshan Sichuan 614000, China

More Information

Author Bio:
E-mail：731484533@qq.com

Corresponding author: E-mail：earlliuh@163.com

摘要

摘要:
我国关键金属铌资源匮乏，被“卡脖子”的风险高，为了破解这一困局，加强新类型铌矿床的研究和地质勘探迫在眉睫。以川南兴文地区上二叠统龙潭组（P₃l）下部黏土岩为研究对象，在样品铌含量分析的基础上，结合粉晶Ｘ射线衍射（XRD）、扫描电镜−能谱（SEM-EDS）、电子探针（EPMA）等手段，对富Nb样品进行了矿物鉴定及定量分析。结果表明，黏土岩中Nb₂O₅质量分数为41×10⁻⁶～437×10⁻⁶，平均187.2×10⁻⁶，达到了风化壳型矿床的最低工业指标，Li、Ga等元素富集程度也较高，是多种关键金属的富集层，具有良好的成矿潜力和找矿前景。粉晶X射线衍射（XRD）分析显示富铌黏土岩中含有较丰富锐钛矿，电子探针（EPMA）分析表明锐钛矿中Nb₂O₅的质量分数为0.09%～3.40%，平均1.17%。依据锐钛矿中铌含量、扫描电镜−能谱（SEM-EDS）扫面，以及全岩样品Nb₂O₅的含量特征，认为铌主要以类质同像形式赋存于锐钛矿之中，还有一部分被黏土矿物所吸附。Nb主要继承自峨眉山玄武岩中榍石等矿物的风化产物，风化作用的强弱对Nb富集成矿具有重要的影响，为风化−沉积型矿床。研究成果为铌资源地质找矿、资源评价以及综合开发利用提供科学依据。
- 铌 /
- 关键金属 /
- 锐钛矿 /
- 赋存状态 /
- 龙潭组 /
- 川南 /
- 兴文地区
Abstract: <p>Niobium is a critical metal, and China faces a high risk of being "strangled" due to the limited availability of niobium. </p></sec><sec><title>Objective
To address this challenge, it is imperative to strengthen the research and geological exploration of new types of niobium deposits.
Methods
This study focuses on the clay rocks in the lower part of the Upper Permian Longtan Formation (P₃l) in Xingwen area of southern Sichuan. Based on the analysis of Nb contents in the collected samples, we combine various analytical techniques such as X-ray powder diffraction (XRD), scanning electron microscopy with energy dispersive spectrometer (SEM-EDS), and electron probe micro-analyzer (EPMA) to conduct mineral identification and quantitative analysis on Nb-enriched samples.
Results
The results show that the content of Nb₂O₅ in the clay rocks ranges from 41×10⁻⁶ to 437×10⁻⁶, with an average of 187.2×10⁻⁶, reaching the lowest industrial indicator for weathering crust-type deposits. The enrichment of elements like Li, Ga, and others is also significant, making the clay layer rich in multiple critical metals and possessing considerable ore-forming potential. XRD analysis reveals a substantial presence of anatase in the Nb-rich clay rock. EPMA analysis indicates that the content of Nb₂O₅ in anatase ranges from 0.09% to 3.40%, with an average of 1.17%. Based on the Nb content in anatase, SEM-EDS scanning, and the Nb₂O₅ content of whole-rock samples, we conclude that Nb primarily exists in anatase as an isomorphous substitution, and some are adsorbed by clay minerals. Nb is predominantly inherited from the weathering products of minerals such as sphene in the Emeishan basalts, and the weathering degree has a significant impact on the enrichment and mineralization of Nb, with characteristic of weathering-sedimentary deposit.
Conclusion
The research results provide a scientific basis for the geological prospecting, resource evaluation, and comprehensive development and utilization of niobium resources.
- niobium /
- critical metal /
- anatase /
- occurrence state /
- Longtan Formation /
- South Sichuan /
- Xingwen area

HTML全文

图 1 峨眉山玄武岩分布示意图^[23] (a)、上二叠统宣威组与龙潭组相变关系图^[29](b)和研究区地质简图(c)

Figure 1. Simplified map showing distribution of the Emeishan basalts(a), phase transition relationship between Xuanwei Formation and Longtan Formation of Upper Permian(b) and geological sketch map of the study area(c)

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图 2 龙潭组下部高岭石黏土岩（矿）石照片

a. 高岭石黏土岩；b～e. 含黄铁矿高岭石黏土岩；b. 团块状黄铁矿；c. 树枝状黄铁矿；d. 褐铁矿化高岭石黏土岩；e. 黄铁矿风化形成褐铁矿仍保留立方体形态；f. 碳质（植物化石）高岭石黏土岩

Figure 2. Photos of typical rocks (ores) in lower part of Longtan Formation

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图 3 ZK03钻孔岩性分层、采样位置及照片

a. 含菱铁矿高岭石黏土岩，水平层理发育；b～f. 含黄铁矿高岭石黏土岩；b. 含鲕粒高岭石黏土岩，见有团块状黄铁矿；c. 含鲕粒高岭石黏土岩的镜下照片（透射光）；d. 见有浸染状黄铁矿；e. 见有星点状黄铁矿；f. 见有树枝状黄铁矿；g. 岩心照片；h. 生物碎屑灰岩。Py. 黄铁矿；P₃l. 上二叠统龙潭组；P₂m. 中二叠统茅口组；下同

Figure 3. Lithologic stratification, sampling location and photos of ZK03 borehole

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图 4 研究区黏土岩Nb₂O₅、Li、Ga (a)及钻孔岩心Nb₂O₅ (b)含量箱形图

Figure 4. Box diagram of Nb₂O₅, Li and Ga contents of clay rocks (a) and Nb₂O₅ content of borehole (b) in the study area

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图 5 ZK03钻孔元素分布图

Figure 5. Variations of of selected elements from ZK03 borehole

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图 6 XRD衍射图谱(a～c)及矿物组分特征(d～f)（2θ. 入射X射线束与衍射探测器之间的夹角）

Figure 6. Diffraction image of XRD (a-c) and mineral composition characteristic (d-f)

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图 7 锐钛矿背散射图（BSE）及电子探针分析点位置图（Py. 黄铁矿）

Figure 7. BSE images and EPMA analyzing points of anatase grains

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图 8 锐钛矿扫描电镜−能谱（SEM-EDS）面扫描

Figure 8. SEM-EDS mapping of anatase grains

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图 9 全部龙潭组岩心样品(a)和部分岩心样品(b)的TiO₂与Nb₂O₅含量相关关系图（R. 皮尔逊相关系数，下同）

Figure 9. Correlation diagram of TiO₂ and Nb₂O₅ content in all core samples (a) and part of core samples (b) of Longtan Formation

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图 10 TiO₂-Al₂O₃二元图^[46]

Figure 10. Binary diagram of TiO₂ vs. Al₂O₃

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图 11 Nb/Ta-Zr/Hf二元图^[32]

Figure 11. Binary diagram of Nb/Ta vs. Zr/Hf

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图 12 CIA与 Nb₂O₅含量相关关系图

Figure 12. Correlation diagram of CIA and Nb₂O₅ content

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表 1 龙潭组下部黏土岩中Nb、Li、Ga元素含量分析结果

Table 1. Analysis results of Nb, Li and Ga in clay rocks of lower part of Longtan Formation w_B/10⁻⁶

样号	Nb₂O₅	Li	Ga	样号	Nb₂O₅	Li	Ga	样号	Nb₂O₅	Li	Ga
CN01-1	309	133	64	CN11-3	226	243	63.5	CN57-2	200	266	52.8
CN02-1	222	68	60.1	CN12-1	212	107	53.3	CN58-2	172	177	60.6
CN02-3	269	143	61.6	CN13-1	139	1482	37.6	CN59-1	176	219	54.3
CN03-1	239	145	56.2	CN14-1	245	224	73	CN64-1	163	40.4	51.1
CN04-1	169	32.5	50.2	CN15-1	166	42.2	52.6	CN68-1	197	84	66.6
CN04-2	245	44.4	52.7	CN16-1	119	51.4	54.7	CN75-2	183	58.5	60.3
CN05-1	115	256	47.6	CN17-2	263	76.6	57.4	CN76-1	89	79.4	26.5
CN05-2	177	186	52.2	CN19-1	176	147	46.8	CN77-1	41	439	43.9
CN06-1	196	115	73.2	CN19-2	217	115	69.2	CN79-1	177	226	47.4
CN06-2	140	46.9	43.9	CN19-3	283	118	64.7	CN80-1	134	235	45.7
CN07-1	222	77.4	68.2	CN20-1	186	80.5	38.5	CN90-1	437	424	61
CN07-2	172	76.9	53.9	CN52-2	154	2053	34
CN08-1	146	33.8	41.5	CN53-2	146	51.3	42.3	平均值	187	223	53.1
CN09-2	93	513	27.4	CN55-2	189	165	67.3	最大值	437	2053	73.2
CN09-4	156	42.4	48.2	CN56-1	115	31.7	52.5	最小值	41	31.7	26.5

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表 2 ZK03钻孔岩心样品化学分析结果

Table 2. Results of chemical analysis of ZK03 borehole

样号	岩性	Al₂O₃	CaO	K₂O	Na₂O	SiO₂	TFe	MgO	MnO	TiO₂	Zr	Hf	Ta	Nb	Nb₂O₅	CIA	Nb/Ta	Zr/Hf	Al₂O₃/ TiO₂
样号	岩性	w_B/%									w_B/10⁻⁶					CIA	Nb/Ta	Zr/Hf	Al₂O₃/ TiO₂
ZK03-3-B1	含菱铁矿高岭石黏土岩	15.96	0.23	1.37	0.45	46.29	16.21	0.71	0.33	2.65	457	11.3	4.42	67.5	96.6	87.74	15.27	40.44	6.02
ZK03-3-B2		16.79	0.5	1.43	0.41	39.67	17.83	0.88	0.37	2.88	482	11.6	4.96	69.2	99	88.26	13.95	41.55	5.83
ZK03-4-B1		19.51	0.72	2.48	0.51	49.15	7.29	1.26	0.31	3.36	690	17.1	7.73	104	149	84.65	13.45	40.35	5.81
ZK03-4-B2		17.44	1.22	1.93	0.54	42.99	11.8	2.15	0.5	2.46	579	14.2	6.18	82.1	117	85.35	13.28	40.77	7.09
ZK03-5-B1	碳质黏土岩夹煤层	21.04	0.17	0.67	0.81	31.92	4.13	0.28	0.032	1.37	1440	34.7	13.2	170	243	91.07	12.88	41.50	15.36
ZK03-6-B1	含黄铁矿高岭石黏土岩	35.1	0.15	0.18	0.28	42.12	1.9	0.041	0.015	2.31	2372	57.8	21.6	287	411	98.15	13.29	41.04	15.19
ZK03-6-B2		36.06	0.068	0.2	0.19	41.51	3.08	0.1	0.004	2.58	1961	47.7	16.5	220	315	98.55	13.33	41.11	13.98
ZK03-6-B3		35.04	0.071	0.15	0.17	40.6	3.25	0.089	0.001	3.06	1880	45.7	17.1	217	310	98.75	12.69	41.14	11.45
ZK03-7-B1		35.08	0.087	0.117	0.117	40.71	3.11	0.15	0.003	3.34	1448	35.8	12	161	230	99.09	13.42	40.45	10.50
ZK03-7-B2		24.09	0.1	0.11	0.12	28.14	16.23	0.15	0.005	2.44	919	22.5	7.72	108	155	98.69	13.99	40.84	9.87
ZK03-7-B3		31.33	0.078	0.14	0.19	36.52	7.84	0.13	0.005	3.41	1293	31.9	10.1	134	192	98.53	13.27	40.53	9.19
ZK03-7-B4		27.98	0.5	0.14	0.21	32.4	11.28	0.11	0.001	3.54	918	22.8	7.89	105	150	98.23	13.31	40.26	7.90
ZK03-7-B5		28.85	0.05	0.11	0.1	43.17	4.81	0.089	0.004	5.56	1233	30.6	10.9	145	207	99.02	13.30	40.29	5.19
ZK03-8-B1	富黄铁矿高岭石黏土岩	12.03	0.053	0.337	0.5	32.43	26.55	0.153	0.008	4.26	800	17.6	7.2	99.8	143	91.01	13.86	45.45	2.82
ZK03-8-B2		9.1	0.048	0.23	0.41	21.25	37.34	0.18	0.008	4.27	716	15.5	7.36	96.3	138	90.77	13.08	46.19	2.13
ZK03-8-B3		13.85	0.091	0.18	0.25	32.61	25.91	0.2	0.013	4.29	843	18.7	8.02	108	155	95.79	13.47	45.08	3.23
ZK03-9-B1	含黄铁矿高岭石黏土岩	24.25	0.13	0.36	0.38	30.58	18.89	0.16	0.008	4.86	885	20.6	8.42	114	163	95.97	13.54	42.96	4.99
ZK03-9-B2	含黄铁矿高岭石黏土岩	35.02	0.13	0.63	0.26	32.55	7.31	0.28	0.22	1.74	401	10.7	3.79	50.5	72.2	96.92	13.32	37.48	20.13
ZK03-10-B1	三水铝石与埃洛石混杂层	50.43	0.197	0.347	0.1	13.09	3.59	0.095	0.54	0.78	182	5.87	1.9	25.2	36.05	98.93	13.26	31.01	64.65
ZK03-11-B1	茅口组灰岩	4.08	45.74	0.08	0.052	2.73	0.75	0.34	0.13	0.19	86.2	1.93	0.998	11.5	16.45
ZK03-11-B2	茅口组灰岩	1.21	50.77	0.07	0.046	1.76	0.49	0.4	0.044	0.13	54.7	1.09	0.79	8.43	12.06
注：CIA. 化学蚀变指数，CIA=[Al₂O₃/（Al₂O₃+CaO+Na₂O+K₂O）]，式中化学成分的含量均为摩尔数，CaO是指存在于硅酸盐矿物中CaO。MECLENNAN等^[31]认为当n（CaO）>n（Na₂O）时，n（CaO）=n（Na₂O），而当n（CaO）<n（Na₂O）时，则n（CaO）=n（CaO），其中n（CaO），n（Na₂O）和n（CaO）分别为CaO，Na₂O和CaO的摩尔数；下同

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表 3 锐钛矿的电子探针定量分析结果

Table 3. EPMA analytical results of anatase grains w_B/%

测试点位	Nb₂O₅	Na₂O	MgO	Al₂O₃	SiO₂	CaO	ZrO₂	FeO	Cr₂O₃	TiO₂	Ce₂O₃	SO₃	V₂O₃	总计
CN90-1-1	1.16	0.01	0.04	0.99	0.58	0.05	0.50	0.31	0.17	93.92	—	0.05	1.14	98.91
CN90-1-2	0.51	0.13	0.01	1.56	1.64	0.06	0.09	0.43	0.44	91.04	0.23	0.09	2.54	98.77
CN90-1-3	0.86	0.07	0.02	1.95	1.54	0.05	1.40	0.71	0.38	90.01	0.06	0.13	1.34	98.49
CN90-1-4	3.40	0.21	0.03	0.80	0.60	0.06	0.15	1.59	0.71	89.95	0.05	0.06	1.01	98.61
CN90-1-5	1.69	—	0.05	2.10	1.84	0.02	0.57	1.23	0.60	81.95	0.05	0.04	8.55	98.68
CN90-1-6	0.95	0.19	0.03	2.23	2.39	0.06	0.09	1.16	0.34	89.23	—	0.05	2.22	98.92
ZK03-6-B1-1	1.84	—	—	0.83	0.78	0.01	0.21	1.21	1.12	90.57	0.19	0.24	2.04	99.03
ZK03-6-B1-2	0.09	0.04	—	0.18	0.03	0.01	0.22	0.83	0.14	95.81	0.04	0.06	1.51	98.94
ZK03-6-B1-3	1.71	—	0.02	0.81	0.42	0.07	1.74	0.40	0.21	92.40	—	0.15	1.21	99.13
ZK03-6-B1-4	1.30	0.08	—	0.68	0.69	0.06	1.18	0.84	0.91	91.09	0.01	0.21	1.52	98.57
ZK03-6-B1-5	1.50	0.04	0.02	1.03	0.86	0.04	0.31	1.27	1.17	89.93	0.17	0.39	2.48	99.22
ZK03-6-B3-1	0.94	0.23	0.05	2.45	2.85	0.06	0.89	0.44	0.50	89.06	—	0.17	1.30	98.92
ZK03-6-B3-2	0.69	0.09	0.02	0.83	0.62	0.05	1.63	0.49	0.45	92.47	—	0.02	1.42	98.78
ZK03-6-B3-3	0.44	—	—	0.67	0.71	0.06	0.51	0.39	0.24	94.93	—	0.07	1.15	99.18
ZK03-6-B3-4	0.39	—	—	2.24	1.80	0.08	0.73	0.26	0.25	91.59	0.07	—	1.10	98.50
平均	1.17	0.07	0.02	1.29	1.16	0.05	0.68	0.77	0.51	90.93	0.06	0.11	2.04	98.84
注：“—”表示测试数据低于检测限

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