扬子北缘埃迪卡拉纪锰矿层中的古氧化还原条件对锰矿成矿过程的影响<sup>&#x0002A;</sup>

doi:10.7605/gdlxb.2025.033

古地理学报 ›› 2025, Vol. 27 ›› Issue (2): 338-350. doi: 10.7605/gdlxb.2025.033

扬子北缘埃迪卡拉纪锰矿层中的古氧化还原条件对锰矿成矿过程的影响^*

王萍¹(), 崔旭¹, 赵海彤², 杜远生³, 栾进华²(), 张雄²^,⁴, 罗旭²^,⁴, 王健¹

1 河南理工大学资源环境学院,河南焦作 454003
2 重庆地质矿产研究院,重大地质事件资源环境效应重庆市重点实验室,重庆 401120
3 中国地质大学(武汉)地球科学学院,湖北武汉 430074
4 重庆华地资环科技有限公司,重庆 401120

收稿日期:2024-09-04 修回日期:2024-10-22 出版日期:2025-04-01 发布日期:2025-04-01
作者简介:
王萍,女,1991年生,博士,讲师,主要从事沉积地质学研究。E-mail: wangping_2016@163.com。
基金资助:
*国家自然科学基金项目(编号: 42202111),生物地质与环境地质国家重点实验室开放基金(编号: GBL22107),河南省博士后基金(编号: HN2022027)和河南省高等学校重点科研项目(编号: 24A170019)资助

Redox conditions of the Ediacaran in northern margin of Yangtze Block and their implications for metallogenic processes

WANG Ping¹(), CUI Xu¹, ZHAO Haitong², DU Yuansheng³, LUAN Jinhua²(), ZHANG Xiong²^,⁴, LUO Xu²^,⁴, WANG Jian¹

1 School of Resources and Environment,Henan Polytechnic University,Henan Jiaozuo 454003,China
2 Chongqing Key Laboratory of Resource and Environmental Effects of Major Geological Events, Chongqing Institute of Geology and Mineral Resources,Chongqing 401120,China
3 School of Earth Sciences,China University of Geosciences(Wuhan),Wuhan 430074,China
4 Chongqing Huadi Resources Environment Technology Co.,LTD.,Chongqing 401120,China

Received:2024-09-04 Revised:2024-10-22 Online:2025-04-01 Published:2025-04-01
About author:
WANG Ping,born in 1991,is a lecturer. Her research interests focus on sedimentary geology. E-mail: wangping_2016@163.com.
Supported by:
Co-funded by the National Natural Science Foundation of China(No.42202111),Open Foundation of State Key Laboratory of Biogeology and Environmental Geology(No. GBL22107),Postdoctoral Foundation of Henan Province(No. HN2022027)and Key Scientific Research Project of Colleges and Universities in Henan Province,China(No.24A170019)

摘要/Abstract

摘要：

扬子板块北缘埃迪卡拉纪锰矿赋存于陡山沱组上部的黑色页岩中,主要分布在城口次级盆地的边缘,目前对于锰矿形成时的氧化还原条件以及成矿模式等问题仍然存在争议,需要进一步研究。对于锰矿的成矿模式,目前主要有2种观点: 一种认为菱锰矿直接从缺氧水体中沉淀,另一种认为水体中的Mn²⁺首先被氧化,然后在沉积物中被还原成菱锰矿。本研究以陡山沱组上部的锰矿层为研究对象,对其进行系统的矿物组成和地球化学分析。结果显示,锰矿层中发现了少量的水锰矿,而水锰矿是一种锰的氧化物矿物,意味着在含锰矿物形成时,存在锰的氧化物中间产物,最终转化为菱锰矿。此外,锰矿层中TOC和TN具有明显的正相关关系,表明地层中的氮主要来源于有机质; TOC与Mn含量具有明显的负相关关系,表明锰矿形成过程中需要消耗有机质; 锰矿层具有很高的 δ¹⁵N 值(+7.22‰~+10.06‰,平均值+9.22‰),可能与有机氮的硝化作用有关,¹⁴N富集的NH₄⁺优先被氧化,导致剩余有机氮具有较高的 δ¹⁵N 值,反映了当时表层水体处于氧化状态。因此,认为陡山沱组锰矿经历了Mn²⁺被氧化然后被还原成菱锰矿的阶段,其成矿过程受到水体氧化还原状态的影响。该研究成果有助于进一步了解埃迪卡拉纪海洋的生物地球化学循环过程。

关键词: 埃迪卡拉系, 陡山沱组, 锰矿, 氧化还原条件, 氮同位素

Abstract:

The Ediacaran manganese deposits located in the northern margin of the Yangtze Block are found within the black shales of the upper Doushantuo Formation,predominantly occurring along the margin of the Chengkou Sub-basin. However,several key issues remain contentious,such as including the redox conditions and the metallogenic processes,which quire further investigation. Two primary metallogenetic models have been proposed: (1)rhodochrosite precipitates directly from an anoxic water column;and(2)dissolved Mn²⁺ is initially oxidized to Mn-oxides,which are then reduced to rhodochrosite within the sediments. This study focuses on the Mn-bearing layers of the Doushantuo Formation,analyzing the high-resolution mineral compositions and geochemical characteristics. The results reveal the presence of minor amounts of manganite,a Mn-oxide mineral,within the manganese deposits. This finding indicates that Mn-oxides likely served as a precursors in the formation of rhodochrosite formation. Additionally,a significant positive correlation between total organic carbon(TOC)and total nitrogen(TN)indicates that nitrogen in the sediments primarily originates from organic matter. Conversely,a negative correlation between TOC and manganese(Mn)content implies that organic matter is consumed during the process of manganese deposition. The Mn-bearing layers are characterized by elevated δ¹⁵N values(+7.22‰ to +10.06‰,mean +9.22‰),which can be attributed to the nitrification of organic nitrogen. During this process,¹⁴N-enriched NH₄⁺ is preferentially oxidized,resulting in an increase in the δ¹⁵N of residual organic nitrogen. This implies that oxic conditions prevailed in the surface waters during the formation of rhodochrosite formation. Therefore,it is concluded that the manganese ore of the Doushantuo Formation underwent a stage of Mn²⁺ oxidation followed by reduction to rhombosite,with its mineralization process being influenced by the redox state of the water. This research further contributes to the understanding of the biogeochemical cycles in the Ediacaran oceans.

Key words: Ediacaran, Doushantuo Formation, manganese deposits, redox conditions, nitrogen isotope

王萍, 崔旭, 赵海彤, 杜远生, 栾进华, 张雄, 罗旭, 王健. 扬子北缘埃迪卡拉纪锰矿层中的古氧化还原条件对锰矿成矿过程的影响^*[J]. 古地理学报, 2025, 27(2): 338-350.

WANG Ping, CUI Xu, ZHAO Haitong, DU Yuansheng, LUAN Jinhua, ZHANG Xiong, LUO Xu, WANG Jian. Redox conditions of the Ediacaran in northern margin of Yangtze Block and their implications for metallogenic processes[J]. Journal of Palaeogeography（Chinese Edition）, 2025, 27(2): 338-350.

http://www.gdlxb.cn/CN/Y2025/V27/I2/338

图/表 7

图1 中—上扬子板块陡山沱组古地理重建图(A;改自Wang et al., 2020)和扬子板块埃迪卡拉系柱状图简图(B)

Fig.1 Palaeogeographic reconstruction of the Doushantuo Fm on the middle-upper Yangtze Block(A;modified from Wang et al., 2020)and the Ediacaran stratigraphic column of the Yangtze Block(B)

图2 重庆高燕锰矿区陡山沱组锰矿床偏光显微照片
A—未见明显结构的锰矿石照片,ZK01-3样品;B—球粒状锰矿石照片,ZK01-11样品;C-D—具有鲕粒结构的锰矿石照片,ZK01-16样品。所有样品均为正交光

Fig.2 Microscope photos of manganese deposits in the Doushantuo Formation of Gaoyan Manganese Deposit,Chongqing

表1 重庆高燕锰矿区ZK-01钻孔陡山沱组锰矿层XRD测试结果

Table1 XRD results of the Mn-bearing layer of Doushantuo Formation in drillcore ZK-01 of Gaoyan Manganese Deposit,Chongqing

样品编号	厚度 /m	石膏 /%	石英 /%	钾长石 /%	斜长石 /%	白云石 /%	黄铁矿 /%	锐钛矿 /%	锰白云石 /%	氟磷灰石 /%	菱锰矿 /%	水锰矿 /%	黏土总量 /%
ZK01-3	14.20		5.3	0.5	2.9	32.9	1.8		4.4		47.2	0.3	4.7
ZK01-7	11.57		13.1		9.5		6.2	0.8	5.5		47.8		17.1
ZK01-11	9.90		8.6			6.3	1.1		3.8		78.4		1.8
ZK01-15	7.80		11.6		1.0	35.0	3.1		33.5		12.0		3.8
ZK01-18	6.07	0.3	16.8		2.9	22.6	3.1	2.8	44.0	1.0	1.3	0.3	4.9
ZK01-22	3.40	0.6	18.1		4.8	29.9	4.4		27.3		5.9		9.0
ZK01-25	1.40		25.0		12.3	7.0	8.7		16.3		3.3		27.4

表2 重庆高燕锰矿区ZK-01钻孔陡山沱组锰矿层地球化学测试结果

Table2 Geochemical results of the Mn-bearing layer of Doushantuo Formation in drillcore ZK-01 of Gaoyan Manganese Deposit,Chongqing

样品编号	厚度 /m	Al₂O₃ /%	MnO /%	δ¹⁵N /‰	TOC /%	TN /%	C/N
ZK01-1	15.12	1.35	29.30	7.12	0.52	0.01	43
ZK01-2	14.97	5.80	11.15	7.75	0.38	0.04	10
ZK01-3	14.20	3.71	33.40	7.82	0.37	0.03	13
ZK01-4	14.04	3.74	38.60	8.63	0.37	0.04	12
ZK01-5	13.64	4.71	28.10	8.59	0.51	0.04	16
ZK01-6	13.17	11.24	4.16	8.30	1.21	0.09	17
ZK01-7	11.57	8.00	20.90	8.62	0.47	0.06	9
ZK01-8	11.17	7.02	18.20	8.29	1.02	0.07	18
ZK01-9	10.75	5.62	27.50	8.37	1.73	0.08	27
ZK01-10	10.40	12.98	11.85	9.00	1.44	0.13	13
ZK01-11	9.90	1.13	37.30	9.46	0.43	0.02	26
ZK01-12	9.20	4.96	23.70	9.58	0.63	0.05	15
ZK01-13	8.70	5.53	21.70	9.75	0.86	0.07	15
ZK01-14	8.30	14.16	6.05	9.37	1.01	0.13	9
ZK01-15	7.80	1.74	29.90	9.62	0.48	0.03	22
ZK01-16	7.20	7.53	11.30	10.03	2.49	0.11	27
ZK01-17	6.67	6.42	15.25	10.58	1.81	0.09	24
ZK01-18	6.07	2.91	23.70	9.85	1.52	0.05	34
ZK01-19	5.87	8.60	12.55	10.60	1.76	0.13	16
ZK01-20	4.40	8.36	8.05	9.01	5.39	0.15	43
ZK01-21	3.90	1.37	31.80	9.65	2.13	0.04	60
ZK01-22	3.40	4.06	20.80	9.89	2.25	0.07	39
ZK01-23	2.90	7.72	10.80	10.11	2.80	0.11	29
ZK01-24	2.40	4.32	19.10	10.01	1.45	0.06	27
ZK01-25	1.40	8.54	6.10	10.44	1.00	0.10	11
ZK01-26	0.40	9.19	2.21	9.41	4.35	0.15	34

图3 重庆高燕锰矿区ZK-01钻孔陡山沱组Ⅳ段锰矿层中Mn含量,TOC,TN,C/N以及 δ¹⁵N 分布情况

Fig.3 Profiles of Mn contents,TOC,TN,C/N and δ¹⁵N values in the Mn-bearing layer of IV Member of Doushantuo Formation in drillcore ZK-01 of Gaoyan Manganese Deposit,Chongqing

图4 重庆高燕锰矿区ZK-01钻孔锰矿层TOC-TN(A),Al₂O₃-δ¹⁵N(B),C/N-TN(C),C/N-δ¹⁵N(D),TOC-δ¹⁵N(E),TN-δ¹⁵N(F),Mn-TOC(G),Mn-TN(H)以及Mn-δ¹⁵N(Ⅰ)二元图解

Fig.4 Cross-plots of TOC-TN(A),Al₂O₃-δ¹⁵N(B),C/N-TN(C),C/N-δ¹⁵N(D),TOC-δ¹⁵N(E),TN-δ¹⁵N(F),Mn-TOC(G),Mn-TN(H)and Mn-δ¹⁵N(I)in drillcore ZK-01 of Gaoyan Manganese Deposit,Chongqing

图5 扬子板块北缘埃迪卡拉系陡山沱组锰矿成矿模式

Fig.5 Metallogenic model of manganese deposits in the Ediacaran Doushantuo Formation,northern margin of Yangtze Block

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扬子北缘埃迪卡拉纪锰矿层中的古氧化还原条件对锰矿成矿过程的影响*

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扬子北缘埃迪卡拉纪锰矿层中的古氧化还原条件对锰矿成矿过程的影响^*