黔西北普宜地区富关键金属元素硫铁矿地质、地球化学和S同位素特征及其对成因的约束

张七道; 肖长源; 李致伟; 李锁明; 孙建勋; 田瑜峰; 李金旺; 李辰

doi:10.19509/j.cnki.dzkq.2021.0086

黔西北普宜地区富关键金属元素硫铁矿地质、地球化学和S同位素特征及其对成因的约束

doi: 10.19509/j.cnki.dzkq.2021.0086

1.
中国地质调查局昆明自然资源综合调查中心, 昆明 650111
2.
中国地质大学(武汉), 武汉 430074

基金项目:

中国地质调查局项目 DD20191012

详细信息

作者简介:
张七道(1986-), 男, 工程师, 主要从事矿产勘查及成矿预测工作。E-mail: 506676421@qq.com

中图分类号: P618.2
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出版历程
- 收稿日期: 2021-04-26
- 网络出版日期: 2022-09-07

Geological, geochemical and sulfur isotopic characteristics of critical metal-enriched pyritic ore in the Puyi area, northwest Guizhou Province: Constraints on the genesis of the deposit

1.
Kunming Comprehensive Natural Resources Survey Center, China Geological Survey, Kunming 650111, China
2.
China University of Geosciences(Wuhan), Wuhan 430074, China

摘要

摘要:
探讨黔西北普宜地区富关键金属元素硫铁矿的同位素地球化学特征、元素地球化学特征及成因, 可以为硫铁矿资源开发、伴生有益元素综合利用与评价及理解富关键金属元素硫铁矿聚集机制提供更为丰富的信息。在全面收集已有地质、矿产资料的基础上, 结合野外实地调查, 应用元素地球化学及硫同位素分析等方法, 对该区硫铁矿地球化学特征及成因做了较为深入研究, 并初步建立成矿模式。结果表明: 富关键金属元素硫铁矿主要赋存于中二叠统龙潭组(P₂l)底部的晶屑凝灰岩中, 矿体形态简单, 呈层状分布, 硫铁矿中共(伴)生的稀土, Li, Nb, Zr, Ga等有益元素均可综合利用。w(ΣREE)平均为431.24×10^-6, 最大值为1 634.57×10^-6, 一般在180×10^-6~1 630×10^-6之间; w(Ga)平均为32.51×10^-6, 一般为25×10^-6~120×10^-6, 最大为120.00×10^-6; w(Nd)平均为103.29×10^-6, 一般为40×10^-6~380×10^-6, 最大为380.00×10^-6; w(Li)最大值为1 366.00×10^-6; w(Al₂O₃)最大值为42.17%。硫铁矿稀土元素配分模式表现为轻稀土元素富集、重稀土元素相对亏损的右倾型。矿石中成矿元素Ga, Li, Zr, Ti, Se, Cd, Nb, V, Hg等元素相对富集, Ba, Sr, Zn, Te等元素相对贫化。硫铁矿石中黄铁矿硫同位素δ³⁴S变化范围主要在-33.90‰~-18.60‰之间, 平均值-16.04‰, 为轻硫富集型, 富关键金属元素硫铁矿的硫源受生物细菌还原作用影响较大。硫铁矿主要是在沉积阶段通过微生物铁还原、微生物硫酸盐还原和化学铁还原驱动下形成的。初步认为赋存于硫铁矿中的稀土主要以类质同象替代形式赋存于黏土矿物中, 形成过程可分为风化搬运阶段、沉积成矿阶段和成岩后生作用阶段。
- 硫铁矿 /
- 硫同位素 /
- 关键金属 /
- 成因 /
- 普宜地区 /
- 黔西北
Abstract:
The study of the isotopic and elemental geochemical characteristics and genesis of critical metal-enriched pyritic ore in the Puyi area of Northwest Guizhou provides more abundant information for the exploitation of pyritic ore resources, comprehensive utilization and evaluation of associated beneficial elements, and understanding the mechanism of critical metal-enriched pyritic ore. Based on the comprehensive collection of existing geological and mineral data, combined with field investigation, the geochemical characteristics and genesis of pyrite in this area are studied by using element geochemistry and sulfur isotope analysis, and the metallogenic model is preliminarily established. The study shows that the critical metal-enriched pyritic ore mainly occurs in the crystalline tuff at the bottom of the Longtan Formation of the middle Permian(P₂l), and the ore body is simple in shape and distributed in layers. The beneficial elements, such as REEs, Li, Nb, Zr, Li, Nb, Zr, Ga, can be comprehensively utilized. The results show that ΣREE usually ranges from 180×10^-6 to 1 630×10^-6, with an average of 431.24×10^-6 and up to 1 634.57×10^-6; Ga usually ranges from 25×10^-6 to 120×10^-6, with an average of 32.51×10^-6 and up to 120.00×10^-6; Nd generally ranges from 40×10^-6 to 380×10^-6, with an average of 103.29×10^-6 and up to 380.00×10^-6; and the maximum values of Li and Al₂O₃ are 1 366.00×10^-6 and 42.17%. The REE distribution pattern of pyritic ore is characterized by enrichment in LREEs and relative depletion in HREEs. The ore-forming elements Ga, Li, Zr, Ti, Se, Cd, Nb, V and Hg are relatively enriched, while Ba, Sr, Zn and Te are relatively depleted. The δ³⁴S of pyrite in pyritic ore mainly range from -33.90‰ to -18.60‰(on average of -16.04‰), which shows the characteristics of the enrichment of light sulfur. The sulfur source of critical metal-enriched pyritic ore was greatly affected by the reduction of biological bacteria. Pyritic ore is mainly formed in the sedimentary stage by microbial iron reduction, microbial sulfate reduction and chemical iron reduction. It is suggested that REEs in pyritic ore mainly occur in clay minerals in the form of similar isomorphic substitution, and the formation process can be divided into the weathering transportation stage, sedimentary mineralization stage and diagenetic epigenetic stage.
- pyritic ore /
- sulfur isotope /
- critical metal /
- genesis /
- Puyi area /
- northwestern Guizhou

HTML全文

图 1 普宜地区地质简图^[21]

1.关岭组；2.嘉陵江组；3.夜郎组；4.长兴组；5.龙潭组；6.茅口组；7.栖霞组；8.梁山组；9.龙马溪组；10.五峰组；11.宝塔组；12.十字铺组；13.湄潭组；14.红花园组；15.桐梓组；16.娄山关组；17.高台组；18.清虚洞组；19.金顶山组；20.明心寺组；21.地质界线；22.断层；23.地点及地名；24.煤；25.铁矿；26.铅锌矿；27.硫铁矿；28.黏土矿; 29.三级构造单元界线；30.四级构造单元界线；31.研究区

Figure 1. Simplified geological map of the Puyi area

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图 2 普宜地区硫铁矿野外产状及矿物结构照片

a.层状黄铁矿；b.团块状黄铁矿(颗粒较大)；c, d.结核状、团块状及草莓状黄铁矿，含较多藻类植物化石；e.星点状黄铁矿；f.晶屑凝灰结构；g.它形-半自形粒状结构；h, i.鲕状结构；Py.黄铁矿

Figure 2. Photographs showing field occurrences and textures of pyritic ore in the Puyi area

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图 3 研究区硫铁矿稀土元素分配模式(球粒陨石标准化数据引自文献[25])

Figure 3. Chondrite-normalized REE patterns in the study area

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图 4 硫铁矿硫同位素组成分布直方图

Figure 4. Histogram of sulfur isotopic compositions of pyritic ore

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图 5 研究区w(B)-w(Ga)(a)和w(Ba)-w(Sr)(b)图解^[29]

Figure 5. B-Ga(a) and Ba-Sr(b) diagrams in the study area

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图 6 限定物源区特征图解(底图据文献[24]修改)

Figure 6. Characteristic diagram of limited source area

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图 7 研究区硫同位素与地球上重要物质及各类硫铁矿床硫同位素组成对比图(底图据文献[49]修改)

TRS.硫酸盐热化学还原；BRS.细菌硫酸盐还原

Figure 7. Comparison of sulfur isotopes in the study area with important substances on the earth and sulfur isotopic compositions of various pyrite deposits

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图 8 研究区富关键金属元素硫铁矿成矿模式图

Figure 8. Metallogenic model map of critical metals enriched pyritic ore in the study area

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表 1 普宜地区硫铁矿石主量元素、微量元素组成及元素比值特征

Table 1. Characteristics of major elements, trace elements and element ratios of pyritic ore in the Puyi area

编号	D4601-1QY	D4630-1QY	D4670-1QY	D4671-1QY	D4672-1QY	D4624-1Y	D4625-1Y	D4630-1Y	D4654-1Y	D4670-1Y	D4671-2Y	D4672-1Y	D4685-1Y	地壳丰度
SiO₂	33.97	29.04	19.78	18.41	36.76	29.27	11.94	40.65	46.58	45.19	32.34	46.88	41.77	28.3
Al₂O₃	29.67	25.32	15.16	14.44	20.94	19.86	7.32	26.10	32.50	31.95	21.06	32.08	29.63	8.41
TFe₂O₃	12.35	13.74	38.72	33.14	15.34	18.83	25.80	13.97	10.30	10.29	19.35	8.72	13.50	5.31
TiO₂	3.43	1.87	2.82	2.24	4.70	1.51	0.26	2.04	1.73	0.99	0.83	2.54	1.16	0.42
CaO w_B/%	0.053	0.055	0.049	0.075	0.075	-	-	-	-	-	-	-	-	4.75
MgO	0.078	0.041	0.11	0.087	0.069	-	-	-	-	-	-	-	-	2.83
Na₂O	0.030	0.120	0.048	0.029	0.039	-	-	-	-	-	-	-	-	2.3
K₂O	0.260	0.450	0.440	0.046	0.150	-	-	-	-	-	-	-	-	1.49
P₂O₅	0.057	0.020	0.037	0.061	0.033	-	-	-	-	-	-	-	-	0.044
烧失量	17.36	27.20	18.88	27.35	18.06	-	-	-	-	-	-	-	-	-
Ni	62.0	35.2	49.5	62.7	49.5	42.5	29.9	45.3	43.7	57.2	76.5	31.2	89.6	59
Co	9.56	23.60	3.61	13.40	11.30	6.54	2.79	3.77	4.79	55.30	13.10	2.43	14.40	27
Cu	62.2	73.4	61.2	158.0	78.2	144.0	36.9	58.9	97.3	61.1	160.0	45.2	104.0	27
Pb	48.6	30.5	47.6	53.8	48.3	129.0	41.9	41.7	34.9	46.5	51.8	30.5	27.5	11
As	4.12	7.82	7.34	4.76	6.44	3.79	< 1.00	15.40	1.04	11.10	4.04	6.40	1.89	2.5
Te	0.28	< 0.20	0.28	0.32	0.84	1.19	0.35	0.75	0.40	0.30	< 0.20	0.38	0.37	-
Se	0.38	0.24	1.54	0.18	3.34	0.76	0.40	1.65	1.57	0.26	0.11	2.32	0.31	0.13
Cr w_B/10^-6	273.0	160.0	148.0	124.0	281.0	185.0	35.6	236.0	197.0	97.3	107.0	636.0	176.0	135
V	280	391	145	261	612	624	104	594	197	129	185	856	266	138
Ga	42.80	41.30	31.60	23.40	32.00	36.90	7.49	40.00	42.40	35.70	28.20	40.80	27.20	16
In	0.380	0.360	0.230	0.140	0.230	0.390	0.078	0.280	0.410	0.058	0.140	0.410	0.320	0.05
Th	8.67	10.40	14.80	9.88	19.10	14.90	2.77	21.80	26.10	13.80	9.53	35.40	20.70	5.6
Zr	1 814	766	1 976	588	1 099	640	116	1 054	1 270	1 830	461	1 430	956	132
Nb	183.0	53.6	194.0	43.2	112.0	42.6	< 5.0	74.4	177.0	168.0	29.7	192.0	64.0	8
U	8.36	5.77	5.62	3.02	8.34	8.63	1.21	7.94	8.39	4.94	1.97	13.40	6.82	1.3
Li	474.0	385.0	150.0	180.0	130.0	133.0	72.4	221.0	723.0	25.5	147.0	200.0	870.0	16
Sr	84.7	41.8	30.9	196.0	27.0	32.7	18.1	47.7	87.5	28.9	177.0	30.0	34.9	320
Cd	0.090	2.220	0.100	1.240	0.460	0.270	0.050	0.130	0.083	2.120	1.410	0.086	0.080	0.08
Ge	2.00	1.12	0.66	0.96	1.14	0.94	0.27	1.10	1.66	1.02	0.79	1.47	1.26	1.3
Ba	30.6	39.8	52.6	157.0	56.2	< 50.0	< 50.0	118.0	70.6	106.0	99.6	99.7	83.0	456
F	370	414	512	410	312	438	368	220	536	571	609	344	817	553
Zn w_B/10^-6	-	-	-	-	-	< 15.0	18.2	< 15.0	< 15.0	75.3	18.7	< 15.0	< 15.0	72
Ag	-	-	-	-	-	0.070	0.033	0.031	< 0.020	0.029	0.076	< 0.020	0.034	0.056
Sb	-	-	-	-	-	2.49	0.36	2.62	1.03	0.98	1.36	3.10	1.11	0.2
Hg	-	-	-	-	-	0.83	0.10	0.77	0.26	0.37	0.43	0.36	0.12	30
B	39.1	42.6	29.8	10.2	12.2	11.7	< 5.00	42.0	45.6	28.9	9.94	25.5	53.4	11
Rb	8.66	7.62	7.98	1.16	2.66	-	-	-	-	-	-	-	-	49
Sc	23.7	22.6	18.5	18.6	24.4	-	-	-	-	-	-	-	-	22
B/Ga	0.91	1.03	0.94	0.44	0.38	0.32	0.67	1.05	1.08	0.81	0.35	0.63	1.96
Sr/Ba	2.77	1.05	0.59	1.25	0.48	0.65	0.36	0.40	1.24	0.27	1.78	0.30	0.42
Th/U	1.04	1.80	2.63	3.27	2.29	1.73	2.29	2.75	3.11	2.79	4.84	2.64	3.04
Rb/K	0.003 3	0.001 7	0.001 8	0.002 5	0.001 8	-	-	-	-	-	-	-	-
Sr/Cu	1.36	0.57	0.50	1.24	0.35	0.23	0.49	0.81	0.90	0.47	1.11	0.66	0.34
V/Cr	1.03	2.44	0.98	2.10	2.18	3.37	2.92	2.52	1.00	1.33	1.73	1.35	1.51
Ni/Co	6.49	1.49	13.71	4.68	4.38	6.50	10.72	12.02	9.12	1.03	5.84	12.84	6.22
Ni/V	0.22	0.09	0.34	0.24	0.08	0.07	0.29	0.08	0.22	0.44	0.41	0.04	0.34
CIA/%	99.03	97.17	96.46	99.40	98.66
Funtion1	11.83	12.88	23.88	20.76	6.72
Funtion2	-6.00	-6.90	-13.63	-13.10	-6.91
注：“-”为未分析项；地壳丰度引自文献[23]; 其中，CIA=[(Al₂O₃)/(Al₂O₃+CaO+Na₂O+K₂O)]×100^[22]; Funtion1=-1.773w(TiO₂)+0.607w(Al₂O₃)+0.76w(TFe₂O₃)-1.5w(MgO)+0.616w(CaO)+0.509w(Na₂O)-1.244w(K₂O)-9.09；Funtion2=0.445w(TiO₂)+0.07w(Al₂O₃)-0.25w(TFe₂O₃)-1.142w(MgO)+0.438w(CaO)+1.475w(Na₂O)+1.426w(K₂O)-6.861^[24]

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表 2 普宜地区硫铁矿石稀土元素含量及特征参数

Table 2. REE content and characteristic parameters of pyritic ore in the Puyi area

样品编号	D4601-1QY	D4630-1QY	D4670-1QY	D4671-1QY	D4672-1QY	D4624-1Y	D4630-1Y	D4654-1Y	D4670-1Y	D4671-2Y	D4672-1Y	D4685-1Y
La	104.0	49.4	93.1	65.6	39.6	78.4	109.0	106.0	86.6	83.5	69.7	43.8
Ce	81.0	39.4	148.0	93.4	79.8	153.0	181.0	172.0	175.0	113.0	177.0	60.1
Pr	14.60	9.43	12.40	14.60	7.49	12.2	15.2	13.6	21.1	21.2	12.3	7.51
Nd	41.20	33.50	31.60	54.40	21.90	33.8	40.0	34.5	83.3	77.6	34.5	25.5
Sm	7.14	11.00	4.06	12.20	4.94	4.68	5.69	5.64	18.2	11.7	10.1	6.62
Eu	1.95	3.33	0.96	3.40	1.22	1.09	1.41	1.62	4.47	2.62	2.59	1.79
Gd	10.10	20.70	5.04	10.30	6.44	4.19	6.87	7.55	16.3	9.23	12.7	8.9
Tb	1.93	3.86	1.10	1.67	1.44	0.83	1.54	1.55	2.81	1.69	2.78	2.06
Dy	11.60	21.40	7.48	9.73	9.44	5.72	10.30	9.28	15.90	10.80	17.60	14.10
Ho w_B/10^-6	2.18	3.92	1.50	1.90	1.90	1.23	2.06	1.68	2.86	2.14	3.4	2.94
Er	6.02	10.60	4.42	5.56	5.84	3.85	6.01	4.56	7.85	6.43	10.1	9.39
Tm	0.80	1.44	0.65	0.81	0.90	0.59	0.9	0.64	1.13	0.94	1.54	1.48
Yb	4.78	8.59	4.24	5.12	6.05	3.98	5.68	3.81	6.92	5.89	9.85	9.62
Lu	0.71	1.30	0.63	0.72	0.91	0.62	0.87	0.57	1.02	0.92	1.51	1.51
Y	56.40	113.00	42.50	54.00	41.40	30.80	54.60	39.10	64.00	65.40	72.70	66.20
ΣREE	344.41	330.87	357.68	333.41	229.27	334.98	441.13	402.10	507.46	413.06	438.37	261.52
LREE	249.89	146.06	290.12	243.60	154.95	283.17	352.30	333.36	388.67	309.62	306.19	145.32
HREE	94.52	184.81	67.56	89.81	74.32	51.81	88.83	68.74	118.79	103.44	132.18	116.20
LREE/HREE	2.64	0.79	4.29	2.71	2.08	5.47	3.97	4.85	3.27	2.99	2.32	1.25
(La/Yb)_N	14.70	3.89	14.84	8.66	4.42	13.31	12.97	18.80	8.46	9.58	4.78	3.08
δEu	0.70	0.66	0.65	0.90	0.66	0.74	0.69	0.76	0.78	0.75	0.70	0.71
δCe	0.43	0.40	0.90	0.68	1.03	1.06	0.93	0.93	0.94	0.62	1.32	0.72
(La/Sm)_N	9.17	2.83	14.43	3.38	5.05	10.54	12.06	11.83	2.99	4.49	4.34	4.16
(Gd/Yb)_N	1.71	1.95	0.96	1.63	0.86	0.85	0.98	1.61	1.91	1.27	1.04	0.75
(La/Ce)_N	3.35	3.27	1.64	1.83	1.29	1.34	1.57	1.61	1.29	1.93	1.03	1.90

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表 3 研究区硫铁矿硫同位素组成

Table 3. Sulfur isotopic composition of pyrite in the study area

样号	矿物	δ³⁴S_V-CDT/‰
TCP05-10TW	黄铁矿	-29.20
D1070-1TW	黄铁矿	-27.40
D3035-1TW	黄铁矿	-33.90
D4601-1TW	黄铁矿	-8.15
D4624-1TW	黄铁矿	6.73
D4625-1TW	黄铁矿	-24.45
D4630-1TW	黄铁矿	-31.43
D4654-1TW	黄铁矿	-18.60
D4661-1TW	黄铁矿	-6.68
D4685-1TW	黄铁矿	9.56
D4729-1TW	黄铁矿	-12.89

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参考文献(87)

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