内蒙古大沟井寒武纪黑色页岩元素地球化学特征及钒赋存形式

doi:10.19657/j.geoscience.1000-8527.2020.054

摘要/Abstract

摘要：

对内蒙古大沟井钒矿床的矿石样品进行了系统的常量和微量元素、X射线粉晶衍射以及显微能谱分析,探讨矿石中钒的赋存形式、形成环境以及保存条件等。研究结果表明,矿石样品中P₂O₅含量变化范围为0.81%~6.14%,显示其磷含量普遍较高,反映地层中较为富集磷;样品烧失量的范围为7.75%~41.24%,比较大,反映云母及泥质胶结物含量较高。矿石的V含量介于1 015.2×10^-6~4 162.0×10^-6之间,远高于地壳中钒的平均含量。U/Th值指示样品为正常的海相沉积产物;矿石的V/Cr、Ni/Co、δU、δCe、Ce/La及V/(V+Ni)值的计算结果以及黑色岩系中的大部分Fe均已转化为黄铁矿这些信息一致揭示出,该区黑色岩系整体上形成于一种较干燥、缺氧、富H₂S、还原和封闭的滞留海盆环境。矿石样品中钒的主要载体矿物为原生矿物相钒云母,为鳞片状矿物,粒度均极细,多型为2M₁,矿物化学分子式为K(V,Al,Mg)₂AlSi₃O₁₀(OH)₂。研究认为大量黄铁矿单晶或集合体的存在是钒元素在黑色岩系中富集和保存的有利因素。

关键词: 赋存状态, 黑色岩系, 钒矿床, 大沟井, 内蒙古

Abstract:

Systematic analysis of ICP-AES, ICP-MS, XRD and EDS was carried out in this paper to discuss the occurrence and distribution of vanadium as well as formation and preservation conditions of the Dagoujing vanadium deposit in Inner Mongolia. The study showed that P₂O₅ contents ranged from 0.81% to 6.14%, and this high phosphor value indicates the enrichment of P in the strata; LOI values ranged from 7.75% to 41.24%, and this high value indicated that mica and argillaceous cement content were high in samples. Vanadium values ranged from 1,015.2×10^-6 to 4,162.0×10^-6, and all the data were much higher than the average composition of the crust. The black shales were classified as normal sedimentary rocks based on the U/Th values; V/Cr, Ni/Co, δU, δCe, Ce/La and V/(V+Ni) values as well as transformation of most of Fe in black shales into pyrite indicated that the black shales in this region formed in a relatively dry, anoxic, H₂S-rich, reducing and close basin condition. Vanadium element in samples mainly occurred in roscoelite, which was in very fine phosphorus shape with polytype 2M₁ and formula K(V,Al,Mg)₂ AlSi₃O₁₀(OH)₂. Occurrence of abundant single or aggregate pyrite in rocks created a favorable condition for vanadium enrichment and preservation in black shales.

Key words: occurrence and distribution, black shale, vanadium deposit, Dagoujing, Inner Mongolia

中图分类号:

P632

张红雨, 苏犁, 秦红. 内蒙古大沟井寒武纪黑色页岩元素地球化学特征及钒赋存形式[J]. 现代地质, 2022, 36(01): 321-332.

ZHANG Hongyu, SU Li, QIN Hong. Element Geochemistry and Vanadium Occurrence of the Dagoujing Black Shales, Inner Mongolia[J]. Geoscience, 2022, 36(01): 321-332.

图/表 11

参考文献 28

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序号	样品编号	采样位置	岩石名称
1	Tc4-3-E1	4号探槽矿层东段	含炭粉砂质板岩
2	Tc4-3-E	4号探槽矿层东段	含炭粉砂质板岩
3	Tc4-3-X	4号探槽矿层下段	粉砂质板岩
4	Tc28-2-E1	28号探槽矿层东段	含炭粉砂泥岩
5	Tc28-2-E3	28号探槽矿层东段	含炭粉砂泥岩
6	Tc28-2-E5	28号探槽矿层东段	含炭粉砂泥岩
7	Tc12-2-X	12号探槽矿层下段	含炭千枚岩
8	Tc12-S	12号探槽矿层上段	含炭千枚岩
9	Tc12-Z	12号探槽矿层中段	含炭千枚岩
10	Zk001-1	1号钻孔113.09~117.09 m	含炭粉砂岩
11	Zk1802	18号钻孔76~80 m	炭质粉砂泥岩
12	Zk301	3号钻孔69.86~72.06 m	含炭粉砂岩
13	Zk501	5号钻孔30.19~31.34 m	含炭粉砂岩

序号	样品编号	采样位置	岩石名称
1	Tc4-3-E1	4号探槽矿层东段	含炭粉砂质板岩
2	Tc4-3-E	4号探槽矿层东段	含炭粉砂质板岩
3	Tc4-3-X	4号探槽矿层下段	粉砂质板岩
4	Tc28-2-E1	28号探槽矿层东段	含炭粉砂泥岩
5	Tc28-2-E3	28号探槽矿层东段	含炭粉砂泥岩
6	Tc28-2-E5	28号探槽矿层东段	含炭粉砂泥岩
7	Tc12-2-X	12号探槽矿层下段	含炭千枚岩
8	Tc12-S	12号探槽矿层上段	含炭千枚岩
9	Tc12-Z	12号探槽矿层中段	含炭千枚岩
10	Zk001-1	1号钻孔113.09~117.09 m	含炭粉砂岩
11	Zk1802	18号钻孔76~80 m	炭质粉砂泥岩
12	Zk301	3号钻孔69.86~72.06 m	含炭粉砂岩
13	Zk501	5号钻孔30.19~31.34 m	含炭粉砂岩

样品编号	SiO₂	TiO₂	Al₂O₃	TFe₂O₃	MnO	MgO	CaO	Na₂O	K₂O	P₂O₅	烧失量	总量
Tc4-3-E1	51.77	0.57	9.03	7.57	0.04	1.21	5.79	0.7	3.03	2.35	13.46	95.52
Tc4-3-E	65.47	0.42	6.65	2.93	0.03	1.11	8.29	0.19	2.4	1.53	9.15	98.17
Tc4-3-X	60.28	0.70	8.73	3.12	0.02	1.44	8.69	0.22	3.43	2.19	7.75	96.58
Tc28-2-E1	65.45	0.82	7.10	5.60	0.01	0.99	4.52	0.25	3.08	1.81	9.02	98.66
Tc28-2-E3	34.65	0.29	3.65	5.64	0.02	0.38	16.09	0.16	0.85	6.14	21.54	89.40
Tc28-2-E5	50.45	0.42	5.91	5.61	0.03	0.81	9.45	0.19	1.96	3.96	16.10	94.90
Tc12-2-X	49.08	0.84	10.30	5.71	0.03	1.62	6.29	0.02	3.67	4.17	17.54	99.26
Tc12-S	63.54	0.91	10.14	6.45	0.03	1.41	3.04	0.20	4.24	0.81	8.54	99.31
Tc12-Z	52.51	0.52	7.96	10.92	0.02	1.27	6.73	0.40	4.16	1.84	11.89	98.20
Zk001-1	40.79	0.41	6.70	4.06	0.02	0.99	1.88	0.08	2.42	1.16	41.24	99.75
Zk1802	54.30	0.77	7.35	4.08	0.02	0.88	8.54	0.29	2.97	2.17	12.74	94.11
Zk301	42.19	0.34	6.75	3.68	0.03	1.50	2.74	0.05	2.49	1.10	38.04	98.90
Zk501	55.89	0.77	11.52	5.95	0.02	2.05	4.46	0.27	4.14	3.20	9.08	97.34

样品编号	SiO₂	TiO₂	Al₂O₃	TFe₂O₃	MnO	MgO	CaO	Na₂O	K₂O	P₂O₅	烧失量	总量
Tc4-3-E1	51.77	0.57	9.03	7.57	0.04	1.21	5.79	0.7	3.03	2.35	13.46	95.52
Tc4-3-E	65.47	0.42	6.65	2.93	0.03	1.11	8.29	0.19	2.4	1.53	9.15	98.17
Tc4-3-X	60.28	0.70	8.73	3.12	0.02	1.44	8.69	0.22	3.43	2.19	7.75	96.58
Tc28-2-E1	65.45	0.82	7.10	5.60	0.01	0.99	4.52	0.25	3.08	1.81	9.02	98.66
Tc28-2-E3	34.65	0.29	3.65	5.64	0.02	0.38	16.09	0.16	0.85	6.14	21.54	89.40
Tc28-2-E5	50.45	0.42	5.91	5.61	0.03	0.81	9.45	0.19	1.96	3.96	16.10	94.90
Tc12-2-X	49.08	0.84	10.30	5.71	0.03	1.62	6.29	0.02	3.67	4.17	17.54	99.26
Tc12-S	63.54	0.91	10.14	6.45	0.03	1.41	3.04	0.20	4.24	0.81	8.54	99.31
Tc12-Z	52.51	0.52	7.96	10.92	0.02	1.27	6.73	0.40	4.16	1.84	11.89	98.20
Zk001-1	40.79	0.41	6.70	4.06	0.02	0.99	1.88	0.08	2.42	1.16	41.24	99.75
Zk1802	54.30	0.77	7.35	4.08	0.02	0.88	8.54	0.29	2.97	2.17	12.74	94.11
Zk301	42.19	0.34	6.75	3.68	0.03	1.50	2.74	0.05	2.49	1.10	38.04	98.90
Zk501	55.89	0.77	11.52	5.95	0.02	2.05	4.46	0.27	4.14	3.20	9.08	97.34

样品编号	Li	Sc	Ti	V	Cr	Mn	Co	Ni	Cu	Zn	Ga
Tc4-3-E1	31.98	12.12	3 210.00	3 362.00	153.30	270.20	34.64	475.80	47.44	114.50	14.88
Tc4-3-E	19.55	8.43	2 338.00	1 767.40	98.70	198.20	4.17	79.42	24.58	58.62	11.38
Tc4-3-X	17.86	9.30	2 754.00	2 362.00	116.30	96.20	1.05	60.38	27.50	28.94	11.82
Tc28-2-E1	17.77	11.70	4 188.00	1 355.80	142.60	99.36	2.65	106.80	67.76	110.50	11.92
Tc28-2-E3	6.72	5.61	1 423.00	774.60	60.16	104.10	0.62	13.19	22.92	49.90	5.76
Tc28-2-E5	16.73	13.24	2 194.00	1 469.60	84.16	178.40	5.85	116.30	33.12	76.10	9.18
Tc12-2-X	29.10	13.26	4 086.00	3 540.00	175.20	199.00	15.38	516.20	130.00	639.80	17.85
Tc12-S	38.04	10.12	4 624.00	1 806.00	156.10	226.80	13.52	391.60	98.72	553.00	15.51
Tc12-Z	26.86	12.30	2 916.00	1 015.20	127.30	183.10	4.06	112.50	41.16	139.80	16.74
Zk001-1	13.89	6.95	2 168.00	3 424.00	85.98	146.50	12.25	435.00	76.24	262.40	16.92
Zk1802	14.58	13.66	3 740.00	3 094.00	133.30	92.62	0.73	38.66	92.50	77.24	12.89
Zk301	24.02	8.37	1 994.20	2 544.00	73.14	202.20	10.91	386.20	42.32	269.00	14.12
Zk501	38.16	14.74	4 016.00	4 162.00	182.00	102.30	4.47	153.80	108.80	36.16	17.76
样品编号	Rb	Sr	Zr	Nb	Cs	Ba	Hf	Ta	Pb	Th	U
Tc4-3-E1	96.86	241.40	196.80	10.61	4.78	449.60	4.19	0.66	38.94	9.66	5.21
Tc4-3-E	84.04	169.60	153.70	8.20	4.08	345.80	2.94	0.50	15.80	4.98	2.32
Tc4-3-X	90.18	81.48	160.40	9.57	4.03	474.80	3.11	0.60	16.56	5.25	2.16
Tc28-2-E1	86.40	363.00	352.20	13.71	4.73	1 624.20	7.31	0.97	47.96	10.08	2.62
Tc28-2-E3	24.08	503.20	87.32	4.67	1.12	4 062.00	1.86	0.29	27.90	3.65	1.87
Tc28-2-E5	50.16	309.00	165.40	7.28	2.00	2 716.00	2.57	0.46	65.58	6.75	1.70
Tc12-2-X	115.90	311.40	301.80	14.34	6.81	1 485.00	6.17	0.90	24.10	10.87	3.73
Tc12-S	130.80	114.80	378.60	15.39	8.78	711.60	8.09	1.09	24.04	10.84	1.93
Tc12-Z	141.70	180.30	144.50	9.63	6.09	864.40	3.13	0.62	14.08	11.00	1.08
Zk001-1	66.04	103.50	106.40	10.63	2.22	2 336.00	2.02	0.46	32.32	5.14	8.54
Zk1802	93.70	85.84	211.40	13.05	8.28	1 059.80	4.22	0.78	30.22	8.31	4.51
Zk301	86.02	98.96	111.00	9.09	4.78	787.40	2.12	0.40	25.56	4.90	7.17
Zk501	127.00	194.40	287.20	14.62	4.18	3 706.00	5.81	0.90	27.86	10.48	3.57