太平洋调查区多金属结核的地球化学特征和成因

doi:10.13745/j.esf.sf.2020.6.37

地学前缘 ›› 2021, Vol. 28 ›› Issue (2): 412-425.DOI: 10.13745/j.esf.sf.2020.6.37

太平洋调查区多金属结核的地球化学特征和成因

任江波(), 邓义楠, 赖佩欣, 何高文(), 王汾连, 姚会强, 邓希光, 刘永刚

1.广州海洋地质调查局自然资源部海底矿产资源重点实验室, 广东广州 510075
2.南方海洋科学与工程广东省实验室(广州), 广东广州 511458

收稿日期:2019-04-15 修回日期:2019-09-18 出版日期:2021-03-25 发布日期:2021-04-03
通讯作者: 何高文
作者简介:任江波(1985—),男,硕士,高级工程师,主要从事地球化学和大洋矿产研究。E-mail: dourjb222@163.com
基金资助:
南方海洋科学与工程广东省实验室(广州)人才团队引进重大专项(GML2019ZD0106);国家自然科学基金项目(41702096);国家自然科学基金项目(41803026);国际海域资源调查与开发“十三五”课题(DY135-R2-1-05);中国地质调查局项目(DD20191009)

Geochemical characteristics and genesis of the polymetallic nodules in the Pacific survey area

REN Jiangbo(), DENG Yinan, LAI Peixin, HE Gaowen(), WANG Fenlian, YAO Huiqiang, DENG Xiguang, LIU Yonggang

1. Ministry of Natural Resources Key Laboratory of Marine Mineral Resources, Guangzhou Marine Geological Survey, Guangzhou 510075, China
2. Southern Marine Science and Engineering Guangdong Laboratory (Guangzhou), Guangzhou 511458, China

Received:2019-04-15 Revised:2019-09-18 Online:2021-03-25 Published:2021-04-03
Contact: HE Gaowen

摘要/Abstract

摘要：

东太结核主要为半埋藏和埋藏型,发育于以黏土和硅质组分为主的沉积环境。东太结核的锰相矿物主要有水羟锰矿和钡镁锰矿,具有较高的REY、Cu、Ni含量和Mn/Fe比值,显示遭受间隙水的影响,落入水成成因和成岩成因两个区间范围。西太结核主体暴露在海水中,周围沉积物主要由深海黏土组成。西太结核的锰相矿物几乎只有水羟锰矿,具有较高的REY、Co含量和低Mn/Fe比值,属于典型的水成成因型。两个区域的多金属结核的稀土北美页岩标准化模式均显示Ce正异常、Y负异常和无或弱Eu异常,与海水稀土特征构成良好的耦合关系,是多金属结核对海水稀土选择性富集的结果。西太结核相对东太结核具有更高的Ce含量和δCe,Co、Ti与Ce具有良好的正相关关系。研究认为海水中溶解氧并不一定是控制结核Ce正异常程度的关键因素,Co、Ti等元素及其相关组分能够引起Ce与其他稀土元素的强烈分馏,也可能是影响多金属结核Ce正异常程度的控制因素。研究区多金属结核和富钴结壳表层样的ε_Nd范围为-6.6~-2.5,是全球最富放射性成因Nd的海洋铁锰壳层。结合稀土模式以及Eu异常特征,本研究认为多金属结核的稀土主要来自ε_Nd相对较高的周围陆壳,可以通过河流或者大气沉降等方式输送到大洋,而研究区广泛分布的海山玄武岩释放的放射性成因Nd同位素对海水的影响微弱。

关键词: 多金属结核, 富钴结壳, 稀土元素, 西太平洋海山区, CC区

Abstract:

The polymetallic nodules in China’s polymetallic nodules exploration contract area in the East Pacific Basin (EP nodules) are largely buried or semi-buried in a sedimentary environment dominated by clay and siliceous components. The manganese mineral phases of the EP nodules mainly include vernadite and todorokite, with high REY and high Cu and Ni contents and Mn/Fe ratio. These characteristics indicate the nodules are affected by interstitial water thus falling into the range of diagenesis and hydrogenesis. In comparison, the polymetallic nodules in the Northwest Pacific Basin (WP nodules) are mostly exposed to seawater, and the surrounding sediments are mainly deep-sea clay. The manganese mineral phases of the WP nodules are almost all vernadite, with high REY, high Co content and low Mn/Fe ratio. It shows that the WP nodules are of typical hydrogenic form. The NASC-normalized REY patterns of the polymetallic nodules in both regions show positive Ce and negative Y anomalies and no/weak Eu anomaly, while the REY patterns of ambient seawater show obvious negative Ce and positive Y anomalies and no obvious Eu anomaly. This inverse coupling relationship implies that the REY patterns of the polymetallic nodules are the result of selective enrichment from seawater. The WP nodules have higher Ce content and δCe than the EP nodules. Both Co and Ti correlate positively with Ce, which may collectively affect the selection of Ce and Y in seawater by polymetallic nodules. In this study, dissolved oxygen in seawater was not a factor controlling the level of positive Ce anomaly observed in the polymetallic nodules. Rather, elements such as Co and Ti and their related components can cause strong fractionation of Ce and other REY, which may be the controlling factor. The surface samples of polymetallic nodules and cobalt-rich crusts in the study area, with ε_Nd values ranging from -6.6 to -2.5, represent the most radioactive ferromanganese samples of Nd in the global sea area. Combining the ε_Nd result with REY patterns and Eu anomaly, we suggest that REY in polymetallic nodules mainly come from the surrounding continental crust with relatively high ε_Nd and can be transported to the ocean via rivers or atmospheric deposition. However, the radioactive Nd isotopes released from basalt in the Northwest Pacific Basin have only weak effect on the seawater.

Key words: polymetallic nodules, Co-rich crusts, rare earth elements, seamounts in western Pacific Ocean, Clarion-Clipperton region

中图分类号:

P736.4
P744

任江波, 邓义楠, 赖佩欣, 何高文, 王汾连, 姚会强, 邓希光, 刘永刚. 太平洋调查区多金属结核的地球化学特征和成因[J]. 地学前缘, 2021, 28(2): 412-425.

REN Jiangbo, DENG Yinan, LAI Peixin, HE Gaowen, WANG Fenlian, YAO Huiqiang, DENG Xiguang, LIU Yonggang. Geochemical characteristics and genesis of the polymetallic nodules in the Pacific survey area[J]. Earth Science Frontiers, 2021, 28(2): 412-425.

图/表 11

图1 太平洋及研究区多金属结核和富钴结壳的站位位置(据文献[5, 8-9, 15-25])

Fig.1 Locations of survey stations for polymetallic nodules and Co-rich crusts in the two study areas and the greater Pacific Ocean. Adapted from [5, 8-9, 15-25].

图2 东、西太平洋多金属结核的岩矿学特征 a—东太结核照片;b—东太结核镜下结构和矿物组分;c—东太结核XRD分析结果;d—西太结核照片;e—西太结核镜下结构和矿物组分;f—西太结核XRD分析结果。

Fig.2 Petrology and mineralogy characteristics of the polymetallic nodules in the East and West Pacific Basins

表1 多金属结核XRD衍射结果

Table 1 XRD diffraction results for the polymetallic nodules

样品	组分含量/%
样品	δ-MnO₂	钡镁锰矿	水钠锰矿	石英	斜长石	正长石	钙十字沸石
东太结核均值	52.1	27.0	0.6	3.1	4.9		12.4
WBC1404-2	49.3	27.2		2.7	2.9		17.9
WBC1419	41.2	35.6	1.1	3.5	16.4		2.3
WBC1423	61.4	24.4	0.8	2.5	3.5		7.4
PRZ1304-BC16	30.9	16.8		5.5	2.3		44.5
西太结核均值	59.0	8.3		9.4	6.5	1.1	12.0
MABC09	81.2			5.8	8.9		4.1
MABC17	79.8			5.5		12.1	2.6
MABD01	38.5	33.2		7.3		8.7	12.3
NBMC01	45.3	15.5		14.8	20.9		3.5

表2 多金属结核和富钴结壳主要化学元素特征对比

Table 2 Comparison of the main geochemical characteristics of the polymetallic nodules and Co-rich crust

样品	参数值类型	w_B/%										w_B/10^-6
		Al₂O₃	SiO₂	P₂O₅	CaO	TiO₂	Mn	Fe	Co	Ni	Cu	Ce	∑REY	δCe	Y/Ho
东太结核	最小值	3.30	12.68	0.30	2.08	0.49	16.78	4.41	0.16	0.32	0.20	217	587	0.96	14.1
	平均值	5.41	15.48	0.56	2.62	1.27	25.00	10.30	0.29	1.07	0.79	588	1 164	1.55	17.3
	最大值	6.96	19.47	1.00	3.46	2.42	32.57	19.09	0.49	1.51	1.61	1 368	2 050	3.17	21.5
西太结核	最小值	3.99	15.23	0.56	2.03	1.37	15.02	11.80	0.31	0.25	0.18	626	1 016	2.28	16.6
	平均值	6.23	18.48	0.71	2.60	2.13	18.01	17.01	0.45	0.42	0.26	1 140	1 751	2.88	18.6
	最大值	9.41	29.02	1.50	3.52	2.67	23.2	21.05	0.55	0.79	0.59	1 556	2 393	3.44	20.9
西太结壳	最小值	0.73	1.94	0.96	3.10	1.28	17.22	9.41	0.23	0.22	0.05	829	1 583	1.31	18.4
	平均值	1.92	7.87	5.85	11.06	1.62	23.11	12.89	0.47	0.46	0.12	1 297	2 392	2.37	29.4
	最大值	4.81	15.27	14.34	23.92	2.2	27.72	16.95	0.72	0.64	0.30	2 001	3 141	3.21	52.6

图3 多金属结核Mn、Fe、Mn/Fe及其他元素间的相关关系(西太结壳数据来自[28],后文图表数据来源同图1)

Fig.3 Correlation among Mn, Fe, Mn/Fe and other elements in the polymetallic nodules (West Pacific crust data adapted from [28])

图4 多金属结核的成因三角判别图(底图据文献[2])

Fig.4 Ternary discrimination diagram for the genesis of the polymetallic nodules. Adapted from [2].

图5 多金属结核REY与δCe、Y/Ho以及P2O5与CaO、Y间的相关关系图

Fig.5 Correlation diagrams for the polymetallic nodules

图6 东太结核(a)和西太结核(b)稀土元素北美页岩标准化图(北美页岩数据据文献[30],洋中脊玄武岩和C1型球粒陨石数据据[31],上陆壳数据据文献[32],海水数据据文献[33])

Fig.6 NASC-normalized REY patterns for the polymetallic nodules in the East (a) and West (b) Pacific Basins. Adapted from [30-33].

图7 多金属结核的稀土特征成因判别图(据文献[4]修改)

Fig.7 Discrimination diagrams for the characteristics and genesis of rare earth elements in the polymetallic nodules. Modified after [4].

图8 多金属结核Ce与Co (a)以及δCe与Co (b)的相关关系

Fig.8 Correlation between Ce and Co (a) or between δCe and Co (b) for polymetallic nodules

图9 多金属结核Ce与TiO2 (a)以及δCe与TiO2 (b)的相关关系

Fig.9 Correlation between Ce and TiO2 (a) or between δCe and TiO2 (b) for polymetallic nodules

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太平洋调查区多金属结核的地球化学特征和成因

Geochemical characteristics and genesis of the polymetallic nodules in the Pacific survey area

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