黄、东海陆架泥质区自生黄铁矿成因及其控制因素

doi:10.11867/j.issn.1001-8166.2020.105

地球科学进展 ›› 2020, Vol. 35 ›› Issue (12): 1306 -1320. doi: 10.11867/j.issn.1001-8166.2020.105

所属专题：地球系统科学大会纪念专刊；

水生关键带有机碳循环过程：从分子水平到全球尺度上一篇

黄、东海陆架泥质区自生黄铁矿成因及其控制因素

常鑫 ¹(

),张明宇 ¹,谷玉 ¹,王厚杰 ^1, ²,刘喜停 ^1, ²(

)

^1.中国海洋大学海洋地球科学学院，海底科学与探测技术教育部重点实验室，山东青岛 266100
^2.青岛海洋科学与技术试点国家实验室海洋地质过程与环境功能实验室，山东青岛 266237

收稿日期:2020-10-16 修回日期:2020-11-20 出版日期:2020-12-10
通讯作者: 刘喜停 E-mail:changxin@stu.ouc.edu.cn;liuxiting@ouc.edu.cn
基金资助:
国家自然科学基金项目“东海内陆架沉积物中自生黄铁矿的形成机制和对环境的响应”(41976053);青岛海洋科学与技术试点国家实验室海洋地质过程与环境功能实验室创新团队建设项目“东海泥质区自生黄铁矿对末次冰消期以来沉积环境演化的响应机制”(MGQNLM-TD201901)

Formation Mechanism and Controlling Factors of Authigenic Pyrite in Mud Sediments on the Shelf of the Yellow Sea and the East China Sea

Xin Chang ¹( ),Mingyu Zhang ¹,Yu Gu ¹,Houjie Wang ^1, ²,Xiting Liu ^1, ²( )

^1.College of Marine Geosciences，Key Laboratory of Submarine Geosciences and Prospecting Technology，Ocean University of China，Qingdao 266100，China
^2.Laboratory for Marine Geology，Qingdao National Laboratory for Marine Science and Technology，Qingdao 266237，China

Received:2020-10-16 Revised:2020-11-20 Online:2020-12-10 Published:2021-02-09
Contact: Xiting Liu E-mail:changxin@stu.ouc.edu.cn;liuxiting@ouc.edu.cn
About author:Chang Xin (1997-), male, Qingdao City, Shandong Province, Master student. Research areas include marine sedimentology. E-mail: changxin@stu.ouc.edu.cn
Supported by:
the National Natural Science Foundation of China “Formation mechanism of authigenic pyrite in the sediments of the East China Sea inner shelf and its response to environmental evolution”(41976053);The Laboratory for Marine Geology, Qingdao Pilot National Laboratory for Marine Science and Technology “Authigenic pyrite in East China Sea mud area constrained by the evolution of sedimentary environment since the last deglaciation”(MGQNLM-TD201901)

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海洋自生黄铁矿的形成过程与有机质矿化过程密切相关，是构成全球C-S-Fe生物地球化学循环的重要一环。黄、东海陆架在全新世高水位期以来，广泛发育泥质沉积区，其中赋存大量自生黄铁矿，为研究其成因及其控制因素提供了契机。平面上，黄铁矿的分布与细粒泥质沉积伴生，因为细粒沉积物相对富集有机质且沉积环境稳定，有利于微生物硫酸盐还原的进行。黄、东海沉积动力、有机质来源和海洋生产力的区别导致黄铁矿生成与埋藏的差异，进而引起相关指标（例如C/S值）的不同。垂向上，黄铁矿的含量一般随着深度的增加而升高，说明随着埋深的增大，孔隙水中溶解氧耗尽后有利于硫酸盐还原的进行；黄铁矿硫同位素随着深度的增加而加重（富集³⁴S），这可能与成岩系统的封闭性有关，也可能与甲烷厌氧氧化驱动的硫酸盐还原有关。另外，沉积速率通过影响有机质的埋藏、孔隙水和海水的联通效率以及硫酸盐—甲烷转换带的位置进而控制黄铁矿的含量及同位素组成。黄、东海陆架泥质区在沉积动力和沉积过程方面积累了大量优秀研究成果，可在此基础上，结合多硫同位素、原位微区测试等先进实验方法，发掘自生黄铁矿在探讨现代海洋C-S-Fe循环及深时海洋化学演化等重大科学问题的潜在价值。

关键词: 自生黄铁矿, 有机碳, 早期成岩, 沉积过程, 硫同位素

The formation process of marine authigenic pyrite （FeS₂） is closely related to the organic mineralization process， representing an important part of the global C-S-Fe biogeochemical cycle. Since the Holocene highstand of sea level， the shelves of the Yellow Sea and the East China Sea have developed mud deposits extensively， in which a large number of authigenic pyrites are present， which provides an opportunity to study their genesis and controlling factors. In terms of spatial distribution， the distribution of pyrite is accompanied by fine-grained mud sediments， because fine-grained sediments are relatively rich in organic matter， and the relatively stable depositional environment is conducive to the progress of microbial sulfate reduction. The differences in sedimentary dynamics， organic matter sources and marine productivity in the Yellow Sea and the East China Sea lead to differences in the formation and burial of pyrite， which in turn cause differences in related indicators （such as the C/S ratio）. In the vertical direction， the content of pyrite generally increases with the increase of depth， indicating that as the depth of burial increases， the dissolved oxygen in the pore water is depleted， which is beneficial to the sulfate reduction； the sulfur isotope of pyrite becomes isotopically heavy with the depth （enrichment of ³⁴S）， which may be related to the openness of the diagenetic system， or the sulfate reduction driven by anaerobic oxidation of methane. In addition， the sedimentation rate controls the content and isotopic composition of pyrite via affecting the burial of organic matter， the efficiency of communication between pore water and seawater， and the location of the sulfate- methane transition zone. The mud areas of the shelves of the Yellow Sea and the East China Sea have accumulated a large number of excellent research results in sedimentary dynamics and sedimentary processes. On this basis， combined with advanced analyzing methods such as multi-sulfur isotopes， in-situ elemental on single pyrite crystal， the potential value of pyrite could be excavated to deal with major scientific issues such as the modern ocean C-S-Fe cycle and deep-time ocean chemical evolution.

Key words: Authigenic pyrite, Organic carbon, Early diagenesis, Sedimentary process, Sulfur isotope

中图分类号:

P736.3

图1 沉积黄铁矿与全球C-S-Fe循环的关系（据参考文献[ 4 ]修改）

Fig.1 The relationship between sedimentary pyrite and global C-S-Fe cycle (modified after reference [ 4 ])

图2 黄、东海泥质区（黄色部分）分布与洋流情况（据参考文献[ 32 , 33 ]修改）
YDW：长江冲淡水；ZMCC：浙闽沿岸流；YSWC：黄海暖流；YSCC：黄海沿岸流；YSMW：黄海混合水；TWC：对马暖流；TWWC：台湾暖流；KC：黑潮

Fig.2 Distribution of mud sediment (yellow) and ocean current system of the Yellow Sea and the East China Sea (modified after references [32,33])
YDW: Yangtze River Diluted Water; ZMCC: Zhe-Min Coastal Current; YSWC: Yellow Sea Warm Current;YSCC: Yellow Sea Coastal Current; YSMW: Yellow Sea Mixing Water; TWC: Tsushima Warm Current;TWWC: Taiwan Warm Current; KC: Kuroshio Current

图3 黄海自生黄铁矿分布及同位素特征（据参考文献[ 31 , 54 , 55 ]修改）
（a）黄海黄铁矿含量等值线平面分布图；（b）H-106孔黄铁矿硫同位素 δ ³⁴S值；YSWC：黄海暖流；YSCC：黄海沿岸流

Fig.3 Distribution and isotopic characteristics of authigenic pyrite in the Yellow Sea (modified after references [31,54,55])
(a) Distribution of pyrite content in mud sediment of the Yellow Sea; (b) Sulfur isotopic compositions of core H-106 derived from the Yellow Sea.YSWC：Yellow Sea Warm Current；YSCC：Yellow Sea Coastal Current

图4 杭州湾YS6钻孔孔隙水剖面（据参考文献[ 59 ]修改）
阴影部分指示SMTZ、硫酸盐还原生成硫化带，钻孔位置见图6

Fig.4 Porewater profile of core YS6 from the Hangzhou Bay (modified after reference [ 59 ])
The shaded part indicates the SMTZ,where sulfide zone is formed by sulfate reduction. The core location is presented in Fig. 6

图5 EC2005钻孔中产出的自生黄铁矿集合体和自生石膏（据参考文献[ 5 , 20 , 21 ]修改）
（a）充填在有孔虫中的生物状自生黄铁矿；（b）管状和他形聚集体；（c)~(e）莓状黄铁矿及表面有溶解坑的八面体微晶；（f）硫化物氧化形成的自生石膏

Fig.5 Authigenic pyrite aggregates and authigenic gypsum of core EC2005 (modified after references [5,20,21])
(a) Authigenic pyrite growing in foraminifera; (b) Tubular and irregular authigenic pyrite aggregates; (c)~(e) Pyrite framboid and octahedral microcrystals with dissolution pits on the surface; (f) Authigenic gypsum caused by sulfide oxidation

图6 东海内陆架自生黄铁矿硫同位素特征（据参考文献[ 20 , 47 ]修改）
（a）东海内陆架泥质区中部分钻孔分布图；（b） EC2005孔中黄铁矿硫同位素与沉积速率的关系；（c）DH5-1、DH7-1中黄铁矿的 δ ³⁴S； δS _CRS指铬还原法测量硫同位素， δS _Pyr指手工挑选黄铁矿测量硫同位素；YDW：长江冲淡水；ZMCC：浙闽沿岸流；TWC：对马暖流

Fig.6 Isotopic characteristics of authigenic pyrite in the inner shelf of the East China Sea (modified after references [20,47])
(a) Core sites from the inner shelf of the East China Sea mentioned in the text;(b) Correlation between pyrite sulfur isotope and sedimentation rate in core EC2005;(c) δ ³⁴S values of pyrite from cores DH5-1 and DH7-1， δS _CRS refers to the measurement of sulfur isotope by chromium reduction method， δS _Pyr means sulfur isotope values of hand-picked macroscopic pyrites. YDW：Yangtze River Diluted Water；ZMCC：Zhe-Min Coastal Current；TWC：Tsushima Warm Current

图7 东海陆架沉积物硫酸盐还原速率和黄铁矿硫埋藏速率与有机碳埋藏速率之间的关系^{［

82
］}

Fig.7 The linear relationship between sulfate reduction rate,pyrite sulfur burial rate and organic carbon burial rate in the East China Sea continental shelf sediments^{[

82
]}

图8 成岩系统的开放程度与黄铁矿相关地球化学参数之间的关系^{[

66
]}

Fig.8 Openness of the diagenetic system and its control on the geochemical parameters related to pyrite^{[

66
]}

图9 体积磁化率反映的SMTZ受沉积速率影响迁移模式图^{[

98
]}

Fig.9 Migration of the SMTZ responding to changes in sedimentation rates indicated by magnetic susceptibility^{[

98
]}

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