太平洋徐福海山富钴结壳稀土元素和铂族元素赋存状态研究

高晶晶; 刘季花; 张辉; 汪虹敏; 崔菁菁; 何连花

doi:10.12284/hyxb2021194

太平洋徐福海山富钴结壳稀土元素和铂族元素赋存状态研究

doi: 10.12284/hyxb2021194

高晶晶^{1, 2,},
刘季花^{1, 2, ,},
张辉^{1, 2},
汪虹敏^{1, 2},
崔菁菁^{1, 2},
何连花^{1, 2}

1.
自然资源部第一海洋研究所自然资源部海洋地质与成矿作用重点实验室，山东青岛 266061
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

基金项目: 国家自然科学基金（40976038）；国际海域资源调查开发“十三五”资源环境课题（DY135-C1-1-04）

详细信息

作者简介:
高晶晶（1980—），女，山东省青岛市人，工程师，主要从事海洋地球化学分析研究。E-mail：gaojingjing8@163.com

通讯作者:
刘季花（1965—），女，研究员，主要从事海洋沉积地球化学研究。E-mail：jihliu@fio.org.cn

中图分类号: P744
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出版历程
- 收稿日期: 2021-06-08
- 修回日期: 2021-08-17
- 网络出版日期: 2021-09-06
- 刊出日期: 2021-12-31

Occurrence phases of rare earth elements and platinum group elements in cobalt-rich crusts from the Seamount Xufu in the Pacific

Gao Jingjing^{1, 2
,},
Liu Jihua^{1, 2
, ,},
Zhang Hui^{1, 2},
Wang Hongmin^{1, 2},
Cui Jingjing^{1, 2},
He Lianhua^{1, 2}

1.
Key Laboratory of Marine Geology and Metallogeny, First Institute of Oceanography, Ministry of Natural Resources, Qingdao 266061, China
2.
Laboratory for Marine Geology, Pilot National Laboratory for Marine Science and Technology (Qingdao), Qingdao 266237, China

摘要

摘要: 利用等离子体发射光谱法、等离子体质谱法以及相态分析手段，对太平洋徐福海山富钴结壳稀土和铂族元素地球化学特征、赋存状态及富集机制进行研究。结果表明，富钴结壳稀土和铂族元素明显富集，其稀土总量为1 842～2 854 μg/g，铂族总量为144～1 180 ng/g，老壳层中稀土和铂族元素含量明显高于新壳层，这可能与老壳层发生磷酸盐化作用有关。轻稀土元素含量明显高于重稀土元素含量，呈现Ce正异常而Eu无异常，具有明显Ce富集特征。铂族元素之间发生了明显分异作用，PPGE含量明显高于IPGE，表现出明显Pt正异常而Pd负异常，具有明显Pt富集而Pd亏损特征。稀土元素赋存状态显示，新壳层中稀土元素主要赋存于铁氧化物相，其富集比例为65.40%～70.05%，老壳层中稀土元素主要赋存于残渣态，富集比例为62.27%～65.77%，这可能与残渣态中磷酸盐有关。铂族元素赋存状态显示，新壳层和老壳层中铂族元素都主要赋存于铁氧化物相，其富集比例为63.66%～69.51%，残渣态(29.20%～34.68%)对铂族元素也有一定的富集能力。富钴结壳稀土和铂族元素的富集推测为铁氧化物胶体粒子的吸附作用，受海水氧化性环境影响，可溶性Ce³⁺和Pt²⁺分别被氧化成不溶性Ce⁴⁺和Pt⁴⁺，沉淀被吸附到铁氧化物相中，从而造成富钴结壳稀土和铂族元素的富集。
- 太平洋 /
- 富钴结壳 /
- 稀土元素 /
- 铂族元素 /
- 赋存状态
Abstract: The geochemistry, occurrence phase and enrichment mechanism of REE and PGE were studied in cobalt-rich crusts from the Seamount Xufu in the Pacific by ICP-OES, ICP-MS and phase analysis methods. The results showed that, REE and PGE were enriched in cobalt-rich crusts, REE contents were 1 842−2854 μg/g, and PGE contents were 144−1180 ng/g. REE and PGE contents in the old layers were higher than that in the new layers, and the phosphatization in the old layers might play an active role in the REE and PGE enrichment. Moreover, LREE contents were more than HREE contents, and REE diagrams showed the positive Ce anomalies and no Eu anomalies, so Ce was enriched in cobalt-rich crusts. Meanwhile, there was an obvious contrast between PGE, and PPGE contents were more than IPGE contents. PGE diagrams showed the positive Pt anomalies and negative Pd anomalies, so Pt was enriched and Pd was poor in cobalt-rich crusts. In addition, REE in the new layers were mainly enriched in the iron oxide phase, and the enrichment ratios were 65.40%−70.05%. While REE in the old layers were mainly enriched in the residual phase, and the enrichment ratios were 62.27%−65.77%, because it might be related to the phosphate. Meanwhile, PGE in the new or old layers were mainly enriched in the iron oxide phase, and the enrichment ratios were 63.66%−69.51%, and also the residual phase ranged from 29.20% to 34.68% had an impact on PGE enrichment. Therefore, REE and PGE enrichment were presumed to the iron oxide colloid particles adsorption. In the marine oxidative environment, the soluble Ce³⁺ and Pt²⁺ were oxidized to insoluble Ce⁴⁺ and Pt⁴⁺ respectively, and the precipitates were adsorbed into the iron oxide phase, so REE and PGE were enriched in cobalt-rich crusts.
- the Pacific /
- cobalt-rich crusts /
- REE /
- PGE /
- occurrence phase

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图 1 富钴结壳XD3样品采集站位位置

Fig. 1 The sampling location of cobalt-rich crust XD3 sample

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图 2 富钴结壳XD3样品分层取样

Fig. 2 The stratified sampling of cobalt-rich crust XD3 smaple

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图 3 富钴结壳不同构造层中稀土元素配分曲线

Fig. 3 REE distribution curves of different structural layer in cobalt-rich crusts

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图 4 富钴结壳不同构造层中铂族元素配分曲线

Fig. 4 PGE distribution curves of different structural layer in cobalt-rich crusts

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图 5 富钴结壳不同构造层中稀土元素赋存状态

Fig. 5 Occurrence phase of REE in different structural layer of cobalt-rich crusts

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图 6 富钴结壳不同构造层中铂族元素赋存状态

Fig. 6 Occurrence phase of PGE in different structural layer of cobalt-rich crusts

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图 7 富钴结壳不同构造层在碳酸盐相、锰氧化物相、铁氧化物相和残渣态中稀土元素配分曲线

Fig. 7 REE distribution curves of carbonate phase, manganese oxide phase, iron oxide phase and residual phase in different structural layer of cobalt-rich crusts

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图 8 富钴结壳不同构造层在碳酸盐相、锰氧化物相、铁氧化物相和残渣态中铂族元素配分曲线

Fig. 8 PGE distribution curves of carbonate phase, manganese oxide phase, iron oxide phase and residual phase in different structural layer of cobalt-rich crusts

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表 1 富钴结壳不同构造层样品描述

Tab. 1 Description of different structural layer in cobalt-rich crusts

样品编号	构造层	深度/mm	样品描述
XD3(I)	第I构造层	0～14	褐黑色，较致密，表层鲕粒状突起，柱状构造
XD3(II)	第II构造层	14～24	黑色，致密，柱状构造
XD3(III)	第III构造层	24～56	黄褐色，疏松，黏土较多，树枝状构造
XD3(IV)	第IV构造层	56～82	黑色，致密，磷酸盐化严重，斑杂状构造
XD3(V)	第V构造层	82～120	亮黑色，致密，较多磷酸盐脉，水平纹状构造

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表 2 富钴结壳不同构造层中稀土元素含量

Tab. 2 REE contents of different structural layer in cobalt-rich crusts

样号	XD3(I)	XD3(II)	XD3(III)	XD3(IV)	XD3(V)	北美页岩
La	277	297	286	309	375	32.0
Ce	820	924	886	1114	1 459	73.0
Pr	58.8	65.3	59.7	65.7	76.4	7.90
Nd	235	256	234	261	302	33.0
Sm	46.8	49.2	47.0	49.6	58.9	5.70
Eu	11.5	12.1	11.3	12.2	14.5	1.24
Gd	58.0	58.2	53.1	60.3	68.5	5.20
Tb	9.31	9.31	8.19	8.71	10.0	0.90
Dy	54.0	53.5	49.2	50.7	59.3	5.80
Ho	10.3	11.3	9.64	10.3	11.7	1.04
Er	32.0	31.6	30.0	29.6	33.7	3.40
Tm	4.57	4.54	4.22	4.16	4.90	0.50
Yb	29.7	28.8	26.8	27.1	31.9	3.10
Lu	4.48	4.35	4.02	4.04	4.76	0.50
Y	191	202	175	306	344	27.0
REE	1 842	2 007	1 885	2313	2 854	200
LREE	1 450	1 604	1 525	1812	2 286	153
HREE	393	403	360	501	568	47.4
LREE/ HREE	3.69	3.98	4.23	3.61	4.02	3.22
Y/Ho	18.4	17.8	18.2	29.7	29.4	26.0
La_N/Yb_N	0.91	1.00	1.04	1.10	1.14	1.00
δCe	1.40	1.44	1.47	1.70	1.87	1.00
δEu	0.97	0.99	0.99	0.98	1.01	1.00
注：表中元素La至HREE含量单位为μg/g；轻稀土元素（LREE）=La+Ce+Pr+Nd+Sm+Eu；重稀土元素（HREE）=Gd+Tb+Dy+Ho+Er+Tm+Yb+Lu+Y；δCe=2Ce_N/(La_N+Pr_N)；δEu=2Eu_N/(Sm_N+Gd_N)；La_N、Ce_N、Pr_N、Sm_N、Eu_N、Gd_N均为北美页岩标准化后的值，北美页岩数据引自文献[27]。

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表 3 富钴结壳不同构造层中铂族元素含量

Tab. 3 PGE contents of different structural layer in cobalt-rich crusts

样号	XD3(I)	XD3(II)	XD3(III)	XD3(IV)	XD3(V)	CI球粒陨石
Os	0.27	0.30	0.50	0.62	0.24	490
Ir	2.79	2.86	3.56	4.79	2.23	455
Ru	7.04	7.06	9.45	13.1	5.34	710
Rh	9.55	8.73	23.8	42.0	10.6	130
Pt	128	123	547	1 114	211	1 010
Pd	1.74	1.56	3.46	5.81	1.74	550
Au	1.31	1.34	1.79	2.81	1.32	140
PGE	150	144	588	1 180	231	232
PPGE	141	135	576	1 164	224	1 830
IPGE	10.1	10.2	13.5	18.5	7.81	1 655
PPGE/IPGE	14.0	13.2	42.6	62.9	28.7	1.11
Pt/Pd	73.8	79.1	158	192	121	1.84
Pt/Ir	46.1	43.2	153.5	232	94.5	2.22
Pd/Ir	0.62	0.55	0.97	1.20	0.78	1.21
Ir/Au	2.14	2.13	1.99	1.71	1.68	3.25
δPt	8.34	8.85	15.9	18.9	13.0	1.00
δPd	0.09	0.08	0.08	0.07	0.07	1.00
注：表中元素Os至IPGE含量单位为ng/g；Pd组（PPGE）=Rh+Pt+Pd+Au；Ir组（IPGE）=Os+Ir+Ru；δPt=${{\rm{Pt}}_{\rm{N}}} $/${ \sqrt{{{\rm{Rh}}}_{{\rm{N}}} \cdot {{\rm{Pd}}}_{{\rm{N}}}}} $；δPd=${ {{\rm{Pd}}}_{{\rm{N}}}} $/${ \sqrt{{\mathrm{P}\mathrm{t}}_{{\rm{N}}} \cdot {\mathrm{A}\mathrm{u}}_{{\rm{N}}}}} $；Rh_N、Pt_N、Pd_N、Au_N均为CI球粒陨石标准化后的值，CI球粒陨石数据引自文献[28]。

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