The study on the early diagenetic processes in REY-rich sediments in Southeast Pacific Ocean and its indicative significance
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摘要: 富稀土深海沉积物作为一种潜在矿产资源，近年来备受关注。研究发现，稀土元素（REY）和钇（Y）元素的富集过程很可能发生在沉积物−海水界面（SWI），但目前针对富稀土沉积物的早期成岩过程研究较少。本研究采集了东南太平洋富稀土海区两个站位的沉积物短柱，解析了REY在SWI的早期成岩过程及其对REY在沉积物中富集机制的影响。孔隙水中较低的Fe、Mn和较高的Mo、U、V浓度表明研究区沉积物处于氧化环境。对比底层海水中REY，孔隙水中的REY呈中稀土（MREE）富集特征。沉积物中REY的主要富集相态为磷酸盐相，而孔隙水中REY及其配分模式可能受控于沉积物中磷酸盐的含量。本研究表明，在稀土元素早期成岩过程中，原本与铁锰相等其他相态结合的REY重新进入到孔隙水中，最终被磷酸盐相吸附和埋藏，早期成岩过程是深海沉积物中REY富集的重要机制。Abstract: As potential mineral resources, rare earth elements (REY) and yttrium enriched sediments in the deep sea have attracted a lot of attention in recent years. It has been shown by studies that the enrichment process of REY is most likely to occur at the sediment-water interface (SWI), however studies on the early diagenetic processes in REY-enriched sediments are in general lacking. In this paper, we collected two short sediment cores in REY-enriched sediments in the Southeast Pacific Ocean, then we had conducted an in-depth analysis on the early diagenesis process of REY at SWI and its influence on the enrichment mechanism of REY in deep-sea sediment. The low Fe, Mn concentration and high Mo, U and V concentration in pore-water indicated that the sediment cores were in oxic environment. Compared to the REY in overlying water column, the dissolved REY in pore-water characterized by a middle rare earth elements (MREE). In sediment, phosphate phase is the main phase of REY, while the distribution pattern of REY in pore-water may be controlled by the phosphate content in sediments. Our results show that during the early diagenetic processes, the REY initially combined with Fe/Mn phase and other phases re-released into the pore-water, which is subsequently adsorbed by and eventually buried with the phosphate phase. Therefore, the early diagenetic process is an important mechanism of REY enrichment in deep sea sediments.
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Key words:
- early diagenetic process /
- pore-water /
- rare earth elements /
- sediment /
- Southeast Pacific Ocean
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图 1 南太平洋水团运移路径[28–30]（a）和南太平洋研究区站位（b）
STSW：亚热带表层水，SAAW：亚南极水，AAIW：南极中层水，NPDW：北太平洋深层水，LCDW：下环极深层水，UCDW：上环极深层水，EUC：赤道潜流。S006、S020海水站位参考自文献[30]
Fig. 1 Water mass migration path in South Pacific Ocean[28–30] (a) and station locations in the study area of South Pacific Ocean (b)
STSW: Subtropical Surface Water, SAAW: Subantarctic Water, AAIW: Antarctic Intermediate Water, NPDW: North Pacific Deep Water, LCDW: Lower Circumpolar Deep Water, UCDW: Upper Circumpolar Deep Water, EUC: Equatorial Undercurrent. Stations S006 and S020 refer to reference [30]
图 2 S014（a, b）、S028（c, d）站位孔隙水中溶解态Fe、Mn和Mo、U、V浓度的垂向分布
Fig. 2 Vertical distributions of dissolved Fe、Mn、Mo、U、V concentration in pore-water of core S014 (a, b) and S028 (c, d)
图 3 孔隙水中稀土元素随深度的变化及PAAS标准化配分曲线
Fig. 3 Variations of REY and PAAS shale-normalized distribution in the pore-water with depth
图 5 沉积物常、微量元素的垂向分布特征
Fig. 5 Vertical distributions of sediment major and trace elements
表 1 标准海水（CASS-5、NASS-6）REY浓度分析结果与前人结果比较以及实验流程平均空白值和检测限（单位：pmol/L）
Tab. 1 The analyzed REY concentrations of certified seawater samples (CASS-5 and NASS-6), compared with the reported values in literature , and average blank value, detection limits of dissolved REY (unit: pmol/L)
元素 CASS-5 NASS-6 空白值(n = 4) 检测限 测试值 报道值a 测试值 报道值b Y 195.6 ± 2.7 – c 225.7 ± 1.4 229.0 ± 23.0 0.61 ± 0.22 0.66 La 57.5 ± 1.8 56.5 ± 1.3 70.4 ± 1.3 74.4 ± 4.3 0.37 ± 0.07 0.22 Ce 24.2 ± 1.1 24.1 ± 2.2 25.6 ± 0.9 30.0 ± 3.8 0.69 ± 0.10 0.29 Pr 8.2 ± 0.1 7.8 ± 1.1 10.6 ± 0.3 11.4 ± 1.1 0.05 ± 0.02 0.06 Nd 37.3 ± 1.2 34.8 ± 1.6 45.6 ± 2.8 46.3 ± 1.4 0.31 ± 0.07 0.21 Sm 8.4 ± 1.1 8.2 ± 0.4 7.8 ± 0.8 8.4 ± 1.2 0.04 ± 0.03 0.08 Eu 1.4 ± 0.1 1.3 ± 0.1 1.7 ± 0.3 1.7 ± 0.2 0.03 ± 0.02 0.05 Gd 8.0 ± 0.7 7.8 ± 1.0 9.6 ± 0.4 8.9 ± 1.3 0.07 ± 0.02 0.07 Tb 1.2 ± 0.1 1.2 ± 0.3 1.5 ± 0.2 1.5 ± 0.1 0.01 ± 0.01 0.02 Dy 7.8 ± 0.3 7.8 ± 0.5 9.5 ± 0.7 10.0 ± 0.5 0.06 ± 0.04 0.12 Ho 2.1 ± 0.1 2.0 ± 0.1 2.6 ± 0.1 2.4 ± 0.2 0.01 ± 0.01 0.02 Er 6.9 ± 0.3 6.4 ± 0.2 8.1 ± 0.4 8.0 ± 0.4 0.03 ± 0.03 0.08 Tm 1.1 ± 0.1 0.9 ± 0.0 1.3 ± 0.2 1.1 ± 0.1 0.01 ± 0.00 0.01 Yb 6.3 ± 0.6 6.3 ± 0.2 7.6 ± 0.3 7.7 ± 0.4 0.02 ± 0.02 0.05 Lu 1.2 ± 0.2 1.1 ± 0.0 1.5 ± 0.3 1.2 ± 0.1 0.01 ± 0.01 0.03 注：数据为平均值 ± 标准偏差；a.基于文献[31–32]计算的CASS-5中REY浓度的平均值；b.基于文献[31–33]计算的NASS-6中REY浓度的平均值；c.未有报道。 
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表 2 标准海水（NASS-6）分析结果
Tab. 2 Analytical results of the reference seawater (NASS-6)
NASS-6 Mo浓度/（nmol·L−1） U浓度/（nmol·L−1） V浓度/（nmol·L−1） 测量值（n = 17） 103.6 ± 4.5 12.8 ± 0.4 30.1 ± 2.5 标准值 103.1 ± 7.5 12.6a 28.7 ± 3.3 a. 未认证，仅供参考（加拿大国家研究委员会）。
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表 3 沉积物中各组分和REY元素含量的皮尔森相关性分析
Tab. 3 Pearson correlation analysis result among other compositions and REY in sediment cores
Al2O3 CaO Fe2O3 MnO P2O5 REY Al2O3 1 CaO −0.85** 1 Fe2O3 0.90** −0.95* 1 MnO 0.43* −0.42* 0.41* 1 P2O5 0.99** −0.85** 0.90** 0.45** 1 REY 0.99** −0.85** 0.90** 0.41* 0.99** 1 注：**相关性在0.01水平上显著（双尾）；*相关性在0.05水平上显著（双尾）。
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