四川雪宝顶W-Sn-Be矿床中矿物化学组成及矿床成因

朱鑫祥; 刘琰

doi:10.15898/j.cnki.11-2131/td.202101100006

四川雪宝顶W-Sn-Be矿床中矿物化学组成及矿床成因

朱鑫祥^1,2,,
刘琰^1, ,

1.
中国地质科学院地质研究所, 北京 100037

2.
中国地质大学(北京), 北京 100083

基金项目:
国家自然科学基金项目（41922014，41772044）；中国地质调查局地质调查项目（DD20190060，DD20190629）

详细信息

作者简介: 朱鑫祥, 硕士, 矿物学、岩石学、矿床学专业, 主要从事稀有金属矿床研究。E-mail: 2120180006@cugb.edu.cn

通讯作者: 刘琰, 博士, 研究员, 矿物学、岩石学、矿床学专业, 主要从事碳酸岩型稀土矿床研究。E-mail: ly@cags.ac.cn

中图分类号: O657.31;O657.63

收稿日期: 2021-01-10

修回日期: 2021-03-07

录用日期: 2021-03-16

刊出日期: 2021-03-28

Chemical Composition of Minerals in Xuebaoding W-Sn-Be Deposit, Sichuan Province: Constraints on Ore Genesis

ZHU Xin-xiang^1,2,,
LIU Yan^1, ,

1.
Institute of Geology, Chinese Academy of Geological Science, Beijing 100037, China

2.
China University of Geosciences(Beijing), Beijing 100083, China

More Information

Corresponding author: LIU Yan, ly@cags.ac.cn

Received Date: 10 January 2021

Revised Date: 07 March 2021

Accepted Date: 16 March 2021

Publish Date: 28 March 2021

摘要

摘要:
雪宝顶矿床位于四川省的松潘甘孜造山带中，以出产大颗粒含W-Sn-Be-F-P的矿物而闻名，前人对该矿床已经开展了大量的研究，但缺乏对粗粒矿物的主次痕量元素研究。本次研究采用X射线荧光光谱（XRF）、电子探针（EMPA）和电感耦合等离子体质谱（ICP-MS）技术对矿床中各矿物的主次痕量元素进行测试分析。结果显示，雪宝顶矿床中的绿柱石、白钨矿、锡石、白云母、萤石、磷灰石、电气石，除富含W、Sn、Be、Na、K、Ca等主要成矿元素外，还富集Li、Rb、Cs等碱金属元素和F、B、P等挥发份。其中，雪宝顶绿柱石中富含Li（3484~4243μg/g）、Rb（39.3~71.1μg/g）、Cs（2955~3526μg/g）；白云母中Li、Rb和Cs元素含量分别高达4243μg/g、72.3μg/g和3526μg/g；磷灰石中除主量元素P外，F（4.48%~5.21%）含量相对较高；电气石中的B含量高达30990~32880μg/g。雪宝顶矿床中的花岗岩岩体W、Sn、Be、Li、Rb、Cs、F、B、P等元素相对富集，但CaO含量（0.46%~0.82%）相对较低。其中Li、F、B、P等元素对成矿元素在成矿流体内的富集起到了极大的促进作用。矿区内大理岩是一种富Ca的方解石大理岩，为成矿提供了大量的Ca元素，有利于粗粒矿物的大规模沉淀。因此，粗粒矿物中的W、Sn、Be、Li、Rb、Cs、F、B、P等元素主要来源于原始岩浆流体，大理岩地层为粗粒矿物提供了大量的Ca元素。
- 雪宝顶 /
- W-Sn-Be矿床 /
- X射线荧光光谱法 /
- 电感耦合等离子质谱法 /
- 电子探针 /
- 化学组成 /
- 矿床成因
Abstract: BACKGROUND
The Xuebaoding deposit, located in the Songpan-Ganzi orogenic belt, Sichuan Province, is famous for coarse-grained W-Sn-Be-F-P-bearing minerals. Many studies have been carried out on this deposit, but there is a lack of research on major and trace elements of coarse-grained minerals.
OBJECTIVES
To obtain major and trace element composition of minerals and provide constraints on ore genesis of the Xuebaoding deposit.
METHODS
In this study, X-ray fluorescence spectrometry (XRF) and electron probe microanalysis (EMPA) were used to analyze the major elements of minerals in the deposit, and the trace elements were analyzed by inductively coupled plasma mass spectrometry (ICP-MS).
RESULTS
The results showed that beryl, scheelite, cassiterite, muscovite, fluorite, apatite and tourmaline in the Xuebaoding deposit were rich in major ore-forming elements (W, Sn, Be, Na, K, Ca) and alkali metal elements such as Li, Rb, Cs, and volatiles such as F, B, and P. Beryl in the Xuebaoding deposit was rich in Li (3484-4243μg/g), Rb (39.3-71.1μg/g) and Cs (2955-3526μg/g). The content of Li, Rb and Cs in muscovite was as high as 4243μg/g, 72.3μg/g and 3526μg/g, respectively. The content of F in apatite and B in tourmaline were 4.48%-5.21% and 30990-32880μg/g, respectively. The granites in the Xuebaoding deposit were relatively rich in W, Sn, Be, Li, Rb, Cs, F, B, P, with relatively low CaO content (0. 46%-0. 82%). Li, Rb, Cs, F, B, P were conducive to the enrichment of ore-forming elements in fluids. Marble in the mining area was calcite marble, which provided a large amount of Ca for mineralization and was conducive to the large-scale precipitation of coarse-grained minerals.
CONCLUSIONS
W, Sn, Be, Li, Rb, Cs, F, B and P in coarse-grained minerals are mainly derived from magmatic fluids, where the marble strata provide a large amount of Ca for coarse-grained minerals.
- Xuebaoding /
- W-Sn-Be deposit /
- X-ray fluorescence spectrometry /
- inductively coupled plasma-mass spectrometry /
- electron probe /
- chemical composition /
- ore genesis

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图 1 盘口、浦口岭花岗岩及上三叠统大理岩地层中的钨锡铍矿化脉简图(据文献[8])

Figure 1.

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表 1 板状绿柱石中主次痕量元素分析测定结果

Table 1. Analytical results of major and trace elements in tabular beryl

主量元素	各样品元素含量(%)
主量元素	Beryl-11	Beryl-12	Beryl-13	Beryl-14	Beryl-15	Beryl-16
SiO₂	63.3	63.2	63.5	63.7	63.4	63.4
TiO₂	0.00	0.02	0.01	0.01	0.01	0.00
Al₂O₃	17.8	17.6	17.9	17.9	17.8	17.8
Fe₂O₃	1.00	0.97	0.98	0.96	1.02	1.02
MnO	0.01	0.02	0.01	0.01	0.01	0.01
MgO	0.08	0.10	0.05	0.06	0.08	0.08
CaO	0.03	0.03	0.03	0.03	0.03	0.03
Na₂O	1.26	1.09	1.07	1.20	1.27	1.38
K₂O	0.04	0.08	0.05	0.06	0.09	0.06
P₂O₅	0.01	0.01	0.01	0.01	0.01	0.01
LOI	2.26	1.96	2.14	2.22	2.22	2.24
总含量	85.8	85.1	85.7	86.2	85.9	86.0

微量元素	各样品元素含量(μg/g)
微量元素	Beryl-11	Beryl-12	Beryl-13	Beryl-14	Beryl-15	Beryl-16
Li	4135	3772	3484	4187	4243	3734
Be	45983	47656	47322	47144	46871	44363
Sc	0.96	2.20	2.68	2.52	2.48	1.84
V	6.93	8.70	7.11	12.4	12.6	8.23
Cr	695	784	573	790	784	739
Co	5.01	6.31	4.70	5.97	6.25	5.66
Ni	21.6	20.4	15.5	19.4	25.7	15.6
Cu	5.80	4.50	4.01	4.08	9.04	9.73
Zn	43.0	23.4	43.9	45.1	52.1	43.7
Ga	15.5	6.77	11.4	18.1	24.2	17.2
Rb	49.3	39.2	52.0	54.7	71.1	51.2
Sr	0.25	0.71	0.43	0.30	0.41	0.27
Y	1.27	1.29	1.29	1.26	1.28	1.26
Nb	0.11	0.13	0.17	0.13	0.19	0.10
Cs	2955	3023	3094	3412	3526	3072
Ba	0.36	0.21	0.65	0.31	0.50	0.16
Ta	0.07	0.13	1.93	0.05	0.15	0.05
Tl	0.33	0.25	0.31	0.36	0.48	0.35
Pb	0.61	0.22	0.15	0.07	0.63	0.10
Bi	0.09	0.02	0.01	0.01	0.07	0.17
Th	0.03	0.00	0.01	0.01	0.04	0.00
U	0.03	0.01	0.03	0.01	0.01	0.00

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表 2 白钨矿中主次痕量元素分析测定结果

Table 2. Analytical results of major and trace elements in scheelite

主量元素	各样品元素含量(%)
主量元素	Scheelite-6	Scheelite-8	Scheelite-9
Ca	13.6	13.4	13.5
Al	< 0.03	< 0.03	0.03
TFe	0.03	0.03	0.04
K	< 0.05	< 0.05	< 0.05
Mg	< 0.01	< 0.01	0.01
Na	0.04	0.03	0.04
W	61.4	62.7	63.1
Si	0.41	0.45	0.36
总含量	75.5	76.6	77.1

微量元素	各样品元素含量(μg/g)
微量元素	Scheelite-6	Scheelite-8	Scheelite-9
Mn	29.1	18.6	18.6
P	< 50	< 50	< 50
V	< 5	< 5	< 5
Li	0.69	0.85	1.12
Be	0.06	0.04	0.18
Sc	0.62	0.65	0.71
Ti	2.35	1.72	1.83
Cr	16.9	< 1	5.6
Co	0.88	0.92	0.97
Ni	14.2	1.9	3.9
Cu	3.33	1.36	2.38
Zn	42.7	7.2	8.6
Rb	0.83	0.54	0.67
Sr	394	150	537
Mo	0.41	0.36	0.18
Ag	0.05	0.21	0.04
In	0.03	0.03	0.02
Cs	0.02	0.01	0.01
Ba	1.94	41.63	47.79
Tl	0.01	0.00	0.00
Pb	14.4	11.4	9.0
Bi	0.88	0.96	1.48
Th	0.39	0.28	0.19
U	0.88	0.34	0.06
Zr	16.1	7.1	12.1
Nb	0.12	0.06	0.07
Hf	0.75	0.33	1.36
Ta	0.07	0.04	0.17
Ga	3.71	2.42	9.54
La	7.54	52.4	44.8
Ce	30.4	171	111
Pr	7.0	28.8	17.6
Nd	43.3	128	71.1
Sm	38.4	39.4	28.9
Eu	6.90	8.16	4.34
Gd	68.2	40.6	31.7
Tb	18.7	8.00	7.74
Dy	115	47.0	47.8
Ho	17.6	8.31	7.75
Er	42.7	21.1	22.2
Tm	4.86	2.66	3.21
Yb	23.6	13.0	18.6
Lu	2.55	1.47	2.04
Y	649	225	379
∑REE	427	570	419
∑REE+Y	1076	795	798

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表 3 磷灰石中主次痕量元素分析测定结果

Table 3. Analytical results of major and trace elements in apatite

主量元素	各样品元素含量(%)
主量元素	Apitite-1	Apitite-2	Apitite-3	Apitite-4	Apitite-5	Apitite-6	Apitite-7
FeO	0.00	0.00	0.00	0.00	0.00	0.00	0.00
Na₂O	0.01	0.00	0.02	0.00	0.00	0.00	0.00
P₂O₅	41.6	41.8	41.9	41.6	42.5	42.0	41.6
Cr₂O₃	0.00	0.00	0.03	0.00	0.00	0.02	0.00
MgO	0.00	0.00	0.00	0.00	0.00	0.00	0.00
CaO	55.3	55.4	55.6	55.5	55.7	55.4	55.8
MnO	0.01	0.00	0.00	0.00	0.02	0.02	0.00
Al₂O₃	0.00	0.00	0.00	0.00	0.00	0.00	0.00
SO₃	0.01	0.00	0.01	0.00	0.00	0.02	0.00
NiO	0.03	0.02	0.02	0.00	0.00	0.02	0.01
SiO₂	0.00	0.00	0.00	0.00	0.00	0.00	0.00
K₂O	0.00	0.01	0.00	0.00	0.00	0.00	0.00
TiO₂	0.00	0.00	0.01	0.00	0.01	0.00	0.00
F	5.21	4.85	4.66	4.90	5.01	4.48	4.62
总含量	99.9	100.0	100.2	99.8	101.1	100.1	100.0

微量元素	各样品元素含量(μg/g)
微量元素	Apitite-1	Apitite-2	Apitite-3	Apitite-4	Apitite-5	Apitite-6	Apitite-7
Li	11.1	8.10	15.8	13.7	21.4	24.0	7.48
Cr	8.59	44.9	3.50	3.80	5.97	4.84	2.37
Co	2.48	3.09	2.63	2.72	2.81	2.64	2.44
Ni	18.1	36.0	16.1	16.4	20.5	19.2	15.7
Cu	6.01	4.08	4.50	3.36	3.37	3.06	2.32
Zn	4.16	1.90	1.38	1.42	2.06	1.02	0.58
Ga	5.80	5.82	6.36	5.25	19.3	6.75	7.94
Rb	2.89	2.75	2.69	6.92	12.7	6.94	1.25
Sr	756	1009	627	1994	1915	2237	2468
Mo	0.20	0.71	0.20	0.16	0.19	0.09	0.12
Cs	0.60	0.58	0.54	1.33	3.65	1.28	0.29
Ba	2.87	3.30	2.39	4.28	10.75	2.23	3.88
Pb	4.86	7.28	8.65	3.89	5.60	3.56	4.01
Bi	0.07	0.17	0.47	0.07	0.06	0.04	0.17
Th	8.23	1.46	4.04	3.01	31.05	4.55	5.64
U	0.33	0.53	0.53	0.42	1.36	0.21	0.72
Nb	0.21	3.88	0.44	0.54	1.24	0.30	0.15
Ta	0.08	0.75	0.13	0.07	0.21	0.07	0.07
Zr	0.61	0.69	0.35	1.15	1.57	0.41	0.43
Hf	0.33	0.29	0.36	0.24	0.54	0.21	0.25
V	0.38	0.56	0.30	0.68	1.08	0.36	0.31
La	129	93.7	153	85.8	910	137	252
Ce	294	246	334	232	1263	328	472
Pr	34.9	30.9	39.8	29.1	116	40.0	52.0
Nd	147	132	172	127	388	172	213
Sm	49.4	43.0	56.4	39.8	90.2	43.3	56.3
Eu	8.10	7.48	6.45	7.81	16.3	9.05	10.1
Gd	58.3	51.7	66.8	44.3	99.1	44.6	60.7
Tb	9.60	9.00	11.6	7.27	17.1	6.74	9.34
Dy	51.3	48.4	62.3	37.7	84.5	33.8	46.8
Ho	8.27	7.64	10.1	6.04	12.4	5.32	7.30
Er	22.2	19.5	27.4	15.2	29.5	13.7	18.3
Tm	2.87	2.31	3.50	1.87	3.05	1.69	2.11
Yb	17.7	13.7	21.1	11.3	16.5	10.4	12.1
Lu	2.29	1.71	2.68	1.49	1.93	1.32	1.55
Sc	1.27	1.39	1.30	1.46	1.42	1.41	1.30
Y	442	426	526	323	505	272	335

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