Geochemistry and Significance of REE and PGE of the Cobalt-Rich Crusts from West Pacific Ocean Seamounts
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摘要: 为了探讨富钴结壳的稀土和铂族元素是否有相似的形成机制，对西太平洋海山富钴结壳稀土和铂族元素进行了类比研究.结果表明：富钴结壳的∑REY范围为1 433.7×10-6~2 888.0×10-6，其中Ce占到近50%，北美页岩标准化后显示较平坦的稀土模式和显著的Ce正异常特征.根据稀土配分模式及已有的Nd同位素结果，富钴结壳具有亲陆壳属性.富钴结壳具有极高的Pt (115.5×10-9~1 132.0×10-9)、(Pt/Pd)N和 (Pt/Os)N值，Ir与Pt及Rh与Pt显示良好相关性.经球粒陨石标准化后显示较一致PGE (platinum-group elements) 配分模式，从Os到Pt逐渐富集，Pd元素强烈亏损.已有的Os同位素研究结果显示物源在地质历史时期从幔源属性向陆源属性变化，但富钴结壳PGE元素内部相对含量仍在一定程度上保持稳定.研究认为：富钴结壳对海水中的稀土清扫具有选择性，Ce的正异常恰恰是结壳对海水稀土中Ce的优先选择造成的，从而导致海水亏损Ce.然而海水中Ce的亏损并未改变新形成富钴结壳的稀土模式，原因是在海洋中存在适量的具有亏损Ce特征的磷酸盐等组分，理论上只需要氧化物类稀土与磷酸盐类稀土消耗的稀土与海水中的补给平衡即可.只是在相关过程中，海洋中氧化物类对稀土的选择更具有主动性，而磷酸盐类表现更多的继承关系.尽管Os同位素显示物源供给发生变化，然而富钴结壳PGE模式相对稳定.因此富钴结壳PGE模式同样可以用富钴结壳对PGE的选择性吸收解释，因富钴结壳优先选择Pt与Ir以及相对排斥Pd和Os，形成了现有独特的PGE模式.Abstract: In order to discuss the differences of the formation mechanism between REE and PGE of the Co-rich Crust, in this study, rare earth elements (REE) and platinum-group elements (PGE) of the Co-rich Crusts from West Pacific Ocean Seamounts are compared and analyzed. The results show that ΣREY of Co-rich crusts ranges from 1 433.7×10-6 to 2 888.0×10-6, in which Ce accounts for nearly 50%. After being shale-normalized, REE patterns display relatively flat models but significant positive Ce anomalies. According to REE patterns and previous Nd isotope results, REE of Co-rich crusts have an affinity with continental crust attribution. Co-rich Crusts are also enriched in PGE and have rather high Pt content (115.5×10-9~1132.0×10-9), high (Pt/Pd)N and (Pt/Os)N ratios, with good correlation between Ir and Pt, Rh and Pt. After being chondrite-normalized, PGE patterns show relatively consistent models characterized by Os to Pt gradual enrichment and Pd element strong loss. Previous Os isotope of Co-rich crusts studies indicate provenance supply changes from mantle source to continental crust source, but the relative amounts of PGE internal elements remain stable in a certain extent. Our studies suggest that Co-rich crusts are selective when enriching rare earth. Ce positive anomaly in Co-rich crusts and Ce loss in seawater is probably due to the fact that Ce in seawater is favored by Co-rich crusts. Ce loss in seawater doesn t change REE patterns of the newly formed Co-rich crusts, and the reason is probably that there is large number of authigenic phosphates characterized by negative anomaly of Ce, which are similar to seawater. In theory, the supply of rare earth in seawater should reach equilibrium with consumption of rare earth in seawater by oxides and phosphates. Importantly in this reaction, the choice of oxides of REE is more active, and phosphates show more inheritance. Despite the provenance supply changing, PGE patterns of Co-rich crusts are still stable. So the fractionation of PGE from seawater to Co-rich Crusts can also be considered for selective PGE absorption. For preference of Pt and Ir, exclusion of Pd and Os, Co-rich Crusts form a unique pattern of PGE.
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Key words:
- REE /
- PGE /
- cobalt-rich crusts /
- West Pacific Ocean Seamounts /
- geochemistry
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图 1 西太平洋海山位置及其时代
洋壳年代据Müller et al.(2008)；海山年代据Koppers et al.(2003)、Koppers and Staudigel(2005)
Fig. 1. Location and age of seamounts in western Pacific Ocean
图 2 富钴结壳成因判别
底图据Halbach et al.(1981)；西太平洋富钴结壳和COMRA结核据何高文 (2006)
Fig. 2. Fe-Mn-10(Ni+Cu) and Fe-Mn-100Co triangular diagrams of Fe-Mn crust genesis
图 3 结壳中REE、PGE与其他元素关系
其他数据任向文 (2005)和卜文瑞
Fig. 3. Plots of REE and PGE vs. other elements of cobalt-rich Fe-Mn crust
图 4 富钴结壳的稀土元素球粒陨石标准化图 (a) 和北美页岩标准化图 (b)
海水数据据Alibo and Nozaki (1999)；北美页岩数据据Gromet et al.(1984)；N-MORB、OIB和球粒陨石数据据Sun and McDonough
Fig. 4. Chondrite-normalized (a) and NASC-normalized (b) REE patterns of cobalt-rich Fe-Mn crust
图 5 富钴结壳的铂族元素球粒陨石标准化
球粒陨石数据据Sun and McDonough (1989)；陆壳数据据Wedepohl (1995)；海水数据据Nozak
Fig. 5. Chondrite-normalized PGE patterns of cobalt-rich Fe-Mn crust
图 6 地质历史时期太平洋海水的Nd同位素特征 (a) 和Os同位素特征 (b)
εNd(0) 图展示近赤道太平洋不同水深富钴结壳的Nd同位素特征，据Van De Flierdt et al.(2004)修改；187Os/188Os图中样品为富金属沉积物，据Klemm et al.(2005)修改
Fig. 6. Nd (a) and Os (b) isotope time-series of Pacific Ocean seawater
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