扬子地块东南缘寒武纪早期黑色页岩容矿的镍钼多金属矿床中黄铁矿原位硫同位素组成及其地质意义<sup>&#x0002A;</sup>

doi:10.7605/gdlxb.2025.048

古地理学报 ›› 2025, Vol. 27 ›› Issue (2): 321-337. doi: 10.7605/gdlxb.2025.048

扬子地块东南缘寒武纪早期黑色页岩容矿的镍钼多金属矿床中黄铁矿原位硫同位素组成及其地质意义^*

侯炳辰¹(), 徐林刚²^,³(), 付勇¹

1 贵州大学资源与环境工程学院, 贵州贵阳 550025
2 中国地质大学(北京)地球科学与资源学院,北京 100083
3 中国地质大学(北京)自然资源部战略性金属矿产找矿理论与技术重点实验室,北京 100083

收稿日期:2024-09-10 修回日期:2024-12-08 出版日期:2025-04-01 发布日期:2025-04-01
作者简介:
侯炳辰,男,2002年生,贵州大学硕士研究生,矿物学、岩石学、矿床学专业。E-mail: 18848004811@163.com。
基金资助:
*国家自然科学基金项目(编号: 41972072,42172080)和黔科合平台项目(编号: KXJZ[2024]016)联合资助

In-situ sulfur isotope compositions of pyrites from the Early Cambrian black shale-hosted polymetallic Ni-Mo deposits in southeastern margin of Yangtze Block and its geological significance

HOU Bingchen¹(), XU Lingang²^,³(), FU Yong¹

1 College of Resources and Enviromental Engineering, Guizhou University, Guiyang 550025, China
2 School of Earth Science and Resources,China University of Geosciences(Beijing),Beijing 100083,China
3 MNR Key Laboratory for Exploration Theory & Technology of Critical Mineral Resources, China University of Geosciences(Beijing),Beijing 100083,China;

Received:2024-09-10 Revised:2024-12-08 Online:2025-04-01 Published:2025-04-01
About author:
HOU Bingchen,born in 2002,is a master degree candidate in mineralogy,petrology,and economic geology. E-mail: 18848004811@163.com.
Supported by:
Co-funded by the National Natural Science Foundation of China(Nos. 41972072,42172080) and Foundation of Department of Science and Technology of Guizhou Province(No. KXJZ[2024]016)

摘要/Abstract

摘要：

扬子地块东南缘寒武系下部黑色页岩容矿的镍钼多金属矿在全球范围内颇具特色,但其成矿过程长期存在争议。本研究通过显微镜和扫描电镜观察识别出3种不同类型的黄铁矿。沉积—成岩早期形成的草莓状黄铁矿(Py1)与钼硫碳集合体(MoSC)和胶状针镍矿共生,黄铁矿原位硫同位素组成 $δ 34 S V - CDT$ 在-12.55‰~10.53‰之间(平均值为-3.38‰,n=25),其硫同位素组成主要受控于海水硫酸盐细菌还原作用。成岩晚期形成的团块状细粒黄铁矿(Py2)集合体硫同位素组成的变化范围在1.98‰~23.54‰之间(平均值为11.88‰,n=16),硫同位素分馏受到受限制沉积盆地的局部硫化环境的影响。热液期形成的粗粒黄铁矿(Py3)与少量脉状针镍矿、脉状闪锌矿、黄铜矿和重晶石共生,说明早期形成的镍钼矿经历的热液叠加成矿作用,黄铁矿硫同位素组成在-21.67‰~-9.73‰之间(平均值为-16.87‰,n=10),反映了热液流体的硫同位素组成特征。沉积—成岩早期形成的黄铁矿与MoSC集合体和胶状针镍矿共生,说明虽然受到热液流体叠加的影响,但是镍和钼主要形成于沉积—成岩早期,寒武纪早期特殊的古海洋环境和海水化学性质依旧是控制镍钼多金属矿形成的主要因素。

关键词: 镍钼多金属矿, 原位硫同位素, 黄铁矿, 寒武纪早期, 黑色页岩, 扬子地块

Abstract:

The polymetallic Ni-Mo deposits hosted in the Early Cambrian black shales are unique worldwide. However,their mineralization processes have long been controversial. Based on detailed microscopic and scanning electronic microscopic observations,we identified three types of pyrites in the sulfide-rich ores. The framboidal pyrites(Py1)formed during the sedimentary-early diagenesis epoch are intergrowth with MoSC compounds and colloidal millerite. In-situ sulfur isotope compositions( $δ 34 S V - CDT$ )of Py1 vary from-12.55‰ to 10.53‰(-3.38‰ on average,n=25). Fractionation of sulfur isotope of Py1 was mainly controlled by bacterial sulfate reduction. The late diagenesis is characterized by fine-grained pyrite aggregates(Py2);their sulfur isotope compositions vary from 1.98‰ to 23.54‰(11.88‰ on average,n=16). Strong sulfur isotope fractionation may be caused by locally sulfidic environments in restricted basins. The coarse-grained pyrites(Py3)formed during the hydrothermal overprinting epoch are intergrowth with millerite and sphalerite veins,chalcopyrite,and barite. Sulfur isotope compositions of Py3 vary from-21.67‰ to-9.73‰(-16.87‰ on average,n=10),which are dominantly a reflection of sulfur isotope compositions of hydrothermal source. The MSC compounds coexist with sedimentary-early diagenesis formed Py1,suggesting that although affected by hydrothermal fluids overprinting,the formation of the polymetallic Ni-Mo sulfide ores was mainly a consequence of unique redox sedimentary environments and chemical compositions during the Early Cambrian.

Key words: polymetallic Ni-Mo deposits, in-situ sulfur isotope, pyrite, Early Cambrian, black shales, Yangtzs Block

侯炳辰, 徐林刚, 付勇. 扬子地块东南缘寒武纪早期黑色页岩容矿的镍钼多金属矿床中黄铁矿原位硫同位素组成及其地质意义^*[J]. 古地理学报, 2025, 27(2): 321-337.

HOU Bingchen, XU Lingang, FU Yong. In-situ sulfur isotope compositions of pyrites from the Early Cambrian black shale-hosted polymetallic Ni-Mo deposits in southeastern margin of Yangtze Block and its geological significance[J]. Journal of Palaeogeography（Chinese Edition）, 2025, 27(2): 321-337.

http://www.gdlxb.cn/CN/Y2025/V27/I2/321

图/表 11

图1 华南寒武纪早期岩相古地理复原图及扬子地块周缘镍钼多金属矿、钒矿、磷矿、重晶石矿和石煤矿空间分布位置(据Lehmann et al., 2016; 有修改)

Fig.1 Early Cambrian palaeogeographic situation of South China with polymetallic Ni-Mo,vanadium,phosphorite,barite,and sapropelite deposition on margin of rifted Yangtze Platform under conditions of sediment-starved marginal basins (modified from Lehmann et al., 2016)

图2 扬子地块东南缘寒武系下部黑色页岩容矿的镍钼多金属矿、钒矿和磷矿矿区地质简图
A—湖南省张家界市三岔地区; B—贵州省遵义市松林地区; C—贵州省毕节市织金县马路河地区; D—贵州省毕节市织金县戈仲伍地区

Fig.2 Geological sketch map of the Early Cambrian black shale-hosted polymetallic Ni-Mo,vanadium, and phosphorite deposits along the southeastern margin of the Yangtze Block

图3 扬子地块东南缘埃迪卡拉系—寒武系下部地层柱状图及典型镍钼多金属矿和磷矿野外照片

Fig.3 Stratigraphic columns from the Ediacaran to Lower Cambrian for southeastern margin of Yangtze Block with photographs showing representative geological features of polymetallic Ni-Mo sulfide and phosphorite deposits

图4 扬子地块东南缘镍钼多金属矿中典型矿物及其生成序次

Fig.4 Typical minerals and their diagenetic sequences in Ni-Mo polymetallic ores in the southeastern margin of Yangtze Platform

图5 扬子地块东南缘镍钼多金属矿石典型扫描电镜照片
注: 根据黄铁矿的形态可划分为3种类型: 草莓状黄铁矿(Py1)、胶状黄铁矿(Py2)和半自形—自形粗粒黄铁矿(Py3)

Fig.5 Representative scanning electronic microscopy images of polymetallic Ni-Mo sulfide ores from the southeastern margin of the Yangtze Block

表1 扬子地块东南缘黑色页岩容矿的镍钼多金属矿中黄铁矿原位硫同位素组成

Table1 Sulfur isotope compositions(δ³⁴S/‰)of different epoch formed pyrites in black shale-hosted polymetallic Ni-Mo sulfide ores from the southeastern margin of Yangtze Block

采样地点	样品编号	黄铁矿形态	黄铁矿形态类型	测试点编号	$δ 34 S V - CDT$ /‰
三岔地区	SC-1-1	团块状、囊状、集合体状	Py2	1	22.23
			Py2	2	13.05
			Py2	3	13.10
	SC-1-2	纹层状、细粒黄铁矿集合体状	Py2	1	22.47
	SC-1-2	纹层状、细粒黄铁矿集合体状	Py2	2	23.54
	SC-2-1	粗粒黄铁矿、亮黄色、半自形—自形结构	Py3	1	-12.63
	SC-2-1	粗粒黄铁矿、亮黄色、半自形—自形结构	Py3	2	-16.21
	SC-2-2	细条带状、黄铁矿集合体,细粒结构	Py2	1	18.74
	SC-2-2	细条带状、黄铁矿集合体,细粒结构	Py2	2	15.31
马路河地区	MLH-1	团块状、囊状、集合体状,细粒黄铁矿	Py2	1	7.86
			Py2	2	7.43
			Py2	3	8.88
	MLH-10-1	粗粒黄铁矿、半自形—自形结构	Py3	1	-20.58
			Py3	2	-20.67
			Py3	3	-18.19
	MLH-10-2	团块状、囊状、集合体状,细粒黄铁矿	Py2	1	9.52
			Py2	2	8.29
			Py2	3	5.12
戈仲伍地区	GZW-1-1	粗粒黄铁矿、亮黄色、他形—半自形结构	Py3	1	-21.67
	GZW-1-2	粗粒黄铁矿、亮黄色、他形—半自形结构	Py3	1	-18.52
	GZW-1-3	粗粒黄铁矿、亮黄色、半自形—自形结构	Py3	1	-13.83
	GZW-1-4	草莓状黄铁矿集合体、暗黄色,发育在MoSC中	Py1	1	-10.04
			Py1	2	-10.19
			Py1	3	-11.50
			Py1	4	-11.66
			Py1	5	-12.55
			Py1	6	-8.86
	GZW-1-5	草莓状黄铁矿集合体、暗黄色,发育在MoSC中	Py1	1	-11.39
	GZW-1-5	草莓状黄铁矿集合体、暗黄色,发育在MoSC中	Py1	2	-11.32
	GZW-1-6	草莓状黄铁矿集合体、暗黄色,发育在MoSC中	Py1	1	5.31
			Py1	2	-6.97
			Py1	3	-9.19
			Py1	4	-9.56
	GZW-1-7	团块状、细条带状	Py2	1	9.25
	GZW-1-7	草莓状黄铁矿集合体、暗黄色,发育在MoSC中	Py1	2	-11.70
	GZW-1-8	草莓状黄铁矿集合体、暗黄色,发育在MoSC中	Py1	1	6.63
			Py1	2	8.37
			Py1	3	8.10
			Py1	4	7.35
			Py1	5	10.53
			Py1	6	0.90
			Py1	7	-4.29
			Py1	8	-4.61
			Py1	9	6.67
			Py1	10	6.31
松林地区	SL-0-1	粗粒黄铁矿,半自形—他形粒状结构	Py3	1	-16.64
	SL-0-2	粗粒黄铁矿,自形—半自形粒状、集合体状	Py3	1	-9.73
	SL-0-3	条带状黄铁矿、亮黄色	Py2	1	3.36
	SL-0-4	细粒黄铁矿、发育在MoSC集合体中	Py1	1	-1.86
		细条带状黄铁矿	Py2	2	1.98
		粗粒黄铁矿集合体	Py1	3	-8.94

表1 扬子地块东南缘黑色页岩容矿的镍钼多金属矿中黄铁矿原位硫同位素组成

Table1 Sulfur isotope compositions(δ³⁴S/‰)of different epoch formed pyrites in black shale-hosted polymetallic Ni-Mo sulfide ores from the southeastern margin of Yangtze Block

采样地点	样品编号	黄铁矿形态	黄铁矿形态类型	测试点编号	$δ 34 S V - CDT$ /‰
三岔地区	SC-1-1	团块状、囊状、集合体状	Py2	1	22.23
			Py2	2	13.05
			Py2	3	13.10
	SC-1-2	纹层状、细粒黄铁矿集合体状	Py2	1	22.47
	SC-1-2	纹层状、细粒黄铁矿集合体状	Py2	2	23.54
	SC-2-1	粗粒黄铁矿、亮黄色、半自形—自形结构	Py3	1	-12.63
	SC-2-1	粗粒黄铁矿、亮黄色、半自形—自形结构	Py3	2	-16.21
	SC-2-2	细条带状、黄铁矿集合体,细粒结构	Py2	1	18.74
	SC-2-2	细条带状、黄铁矿集合体,细粒结构	Py2	2	15.31
马路河地区	MLH-1	团块状、囊状、集合体状,细粒黄铁矿	Py2	1	7.86
			Py2	2	7.43
			Py2	3	8.88
	MLH-10-1	粗粒黄铁矿、半自形—自形结构	Py3	1	-20.58
			Py3	2	-20.67
			Py3	3	-18.19
	MLH-10-2	团块状、囊状、集合体状,细粒黄铁矿	Py2	1	9.52
			Py2	2	8.29
			Py2	3	5.12
戈仲伍地区	GZW-1-1	粗粒黄铁矿、亮黄色、他形—半自形结构	Py3	1	-21.67
	GZW-1-2	粗粒黄铁矿、亮黄色、他形—半自形结构	Py3	1	-18.52
	GZW-1-3	粗粒黄铁矿、亮黄色、半自形—自形结构	Py3	1	-13.83
	GZW-1-4	草莓状黄铁矿集合体、暗黄色,发育在MoSC中	Py1	1	-10.04
			Py1	2	-10.19
			Py1	3	-11.50
			Py1	4	-11.66
			Py1	5	-12.55
			Py1	6	-8.86
	GZW-1-5	草莓状黄铁矿集合体、暗黄色,发育在MoSC中	Py1	1	-11.39
	GZW-1-5	草莓状黄铁矿集合体、暗黄色,发育在MoSC中	Py1	2	-11.32
	GZW-1-6	草莓状黄铁矿集合体、暗黄色,发育在MoSC中	Py1	1	5.31
			Py1	2	-6.97
			Py1	3	-9.19
			Py1	4	-9.56
	GZW-1-7	团块状、细条带状	Py2	1	9.25
	GZW-1-7	草莓状黄铁矿集合体、暗黄色,发育在MoSC中	Py1	2	-11.70
	GZW-1-8	草莓状黄铁矿集合体、暗黄色,发育在MoSC中	Py1	1	6.63
			Py1	2	8.37
			Py1	3	8.10
			Py1	4	7.35
			Py1	5	10.53
			Py1	6	0.90
			Py1	7	-4.29
			Py1	8	-4.61
			Py1	9	6.67
			Py1	10	6.31
松林地区	SL-0-1	粗粒黄铁矿,半自形—他形粒状结构	Py3	1	-16.64
	SL-0-2	粗粒黄铁矿,自形—半自形粒状、集合体状	Py3	1	-9.73
	SL-0-3	条带状黄铁矿、亮黄色	Py2	1	3.36
	SL-0-4	细粒黄铁矿、发育在MoSC集合体中	Py1	1	-1.86
		细条带状黄铁矿	Py2	2	1.98
		粗粒黄铁矿集合体	Py1	3	-8.94

图6 湖南省张家界市三岔地区镍钼多金属矿中黄铁矿形态特征及原位硫同位素组成

Fig.6 Morphology and in-situ sulfur isotope composition of pyrites from the Sancha polymetallic Ni-Mo sulfide deposit at Zhangjiajie,Hunan Province

图7 贵州省毕节市织金县马路河地区镍钼多金属矿中黄铁矿形态特征及原位硫同位素组成

Fig.7 Morphology and in-situ sulfur isotope composition of pyrites from the Maluhe polymetallic Ni-Mo sulfide deposit at Zhijin,Bijie,Guizhou Province

图8 贵州毕节市织金县戈仲伍地区镍钼多金属矿中黄铁矿形态特征及原位硫同位素组成

Fig.8 Morphology and in-situ sulfur isotope composition of pyrites from the Gezhongwu polymetallic Ni-Mo sulfide deposit at Zhijin, Bijie,Guizhou Province

图9 贵州省遵义市松林地区镍钼多金属矿中黄铁矿形态特征及原位硫同位素组成

Fig.9 Morphology and in-situ sulfur isotope composition of pyrites from the Songlin polymetallic Ni-Mo sulfide deposit at Zunyi,Guizhou Province

图10 扬子地块东南缘镍钼多金属矿中黄铁矿原位硫同位素频数分布直方图

Fig.10 Frequence histogram of in-situ sulfur isotope compositions of pyrites from polymetallic Ni-Mo sulfide deposits at the southeastern margin of Yangtze Block

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扬子地块东南缘寒武纪早期黑色页岩容矿的镍钼多金属矿床中黄铁矿原位硫同位素组成及其地质意义^*

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