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Enrichment and geochemical characteristics of rare earth elements in deep-sea mud from seamount area of Western Pacific

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40 sediment samples were collected in 18 stations from seamounts areas in Western Pacific and from CC zone in Central Pacific. Based on the measurements of main elements and minor elements including Rare Earth Elements (REEs), the geochemical characteristics of REE enrichment in zeolitic clay were analyzed. The zeolitic clay was found to be distributed mainly at Marshall Seamounts and Line Islands, marked by high content of metal elements and especially of REEs. The observed highest content of REE in zeolitic clay was 1018.84 μg·g-1, with the highest ∑LREE of 781.00 μg·g-1, and the highest ∑HREE of 237.84 μg·g-1, which were comparable to or even greater than REEs content from the southern China ion-absorption-type deposits. The normalizd REEs with North American Shale Composite (NASC) in zeolitic clay displayed gentle slope, distinct negative Ce anomaly and fractionation of HREE and LREE, which suggested that combined effect of hydrothermally Fe-Mn oxyhydroxides and mixture of phosphatic mineral formed during early diagenesis are possible mechanism of REEs enrichment in zeolitic clay, but needs further study.
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31 6
Vol. 31 No. 6
JOURNAL OF THE CHINESE SOCIETY OF RARE EARTHS
2013 12
Dec. 2013
收稿日期2013 05 30修订日期2013 09 -06
基金项目浙江大学海洋学科交叉研究引导基金项 2012HY006A 国家自然科学基金 40706057 大洋专项基金 DY125-14-R-
01 973 项目 2012CB417305资助
作者简介张霄宇 1972 副教授研究方向地球化学
*通讯联系人E mailzhang_xiaoyu@ zju. edu. cn
DOI10. 11785 / S1000 4343. 20130614
西太平洋海山区深海软泥中稀土元素富集的地球化学特征
张霄宇1* 1张富元2章伟艳2 1江彬彬1
1. 浙江大学地球科学系浙江 杭州 3100272. 国家海洋局第二海洋研究所海底科学重点实验室浙江
杭州 310012
摘要对西太平洋海山区和东太平洋 CC 18 个站位 40 个沉积物样品进行了元素测定以探讨西太平洋海山区含沸石深海粘土中稀土元素
富集的地球化学特征和可能的富集机制
西太平洋海山区沉积物类型复杂含沸石型深海粘土中富含各类微量元素尤其以稀土元素富集程
度最大接近或高于中国南方离子吸附型稀土矿床含沸石型深海粘土主要分布在马绍尔和莱恩群岛REE 最高达1018. 84 μg·g 1 其中
LREE 781. 00 μg·g 1 HREE 237. 84 μg·g-1
平缓的北美页岩归一化模式
显著的δCe 负异常
以及轻中重稀土分馏特征表明热液
铁锰水合物以及早期成岩的含磷矿物混入是造成含沸石深海粘土中稀土元素富集的可能机制
含沸石型深海沉积物 REE 的具体富集机制
还需要做进一步的研究
关键词西太平洋海山区含沸石深海粘土富集特征稀土
中图分类号P736. 21 文献标识码A文章编号1000 4343 201306 0729 09
20 世纪 80 年代以来持续的结壳1 3
热液
硫化物的研究热点4 6形成鲜明对比的是大洋广
泛分布的海底软泥中可能赋存的金属矿产资源一
直以来没有受到足够的重视2011
78 个柱样沉积在深上以 1米间隔取样
检测了 2037 个沉积物样品的元素组成认为在南
太平洋东部和北太平洋中部的软泥中富含有大量
稀土元素和金属钇在含量最高的一个站位周围 1
km2范围内储存的稀土元素资源可提供世界稀土
元素1 /5 的需求量认为热液铁锰水合物和沸石可
能是稀土元素的主要赋存矿物相7
由此深海沉
积物作为稀土元素重要赋存地质体引起了全世界
的关注
实际上20 世纪 70 年代Piper8就指出
太平洋含沸石的深海沉积物中富含了 5倍于北美
页岩的 REE并且长期以来钙十字沸石被认为是
深海沉积物主要 REE 赋存体之一
但是钙十
字沸石与高 REE 含量之间的确切关系至今没有得
到很 Bernat9研究表明沸石本身
LREE 的含量不到 NASC 1 /3Dubinin10在深入
研究了沸石晶中 REE 的富集过程后认沸石
本身并不能吸 REE对太平洋两个站位沉积物
50 μm的沸石 REE 含量的检测结果也仅为
NASC 2 3
由此可见目前关于含沸石深海沉积物中稀
土元素的地球化学特征研究较少其富制也
尚不完全
但是作为火山碎屑海解作用的产
沸石是深海沉积物一个主要矿物成其含量
甚至可以达到 50% 11因此沸石对沉积物中元
素组成显然有着重要影响8
本文以西太平洋海
山区含沸石深海粘土为主要研究对象在进行了
常量元素
稀土元素和微量元素测试分析的基础
1分析西太平洋海山区不同类型沉积物中稀
土元素和其他微量元素富集程度 2含沸石深海
730 31
粘土中稀土元素赋存的地球化学特征 3初步探
含沸石深海粘土中稀土元素的可能富集机制
从而为我国在太平洋海山区沉积物金属矿产资源
的研究提供基础
这对勘查除了结壳
热液硫化物等海洋资源以外的潜在的金属元素赋
存体无疑具有重要的意义对未来我国稀土资源
在全球分布格局中的战略地位有着深刻的
影响
1采样及方法
本次究在西太平洋麦哲伦海山区
马绍尔
群岛
莱恩群东太 CC 区共布设了 18
个站位进行表层沉积物样品的采集对部分站位
在垂直剖面上分别以10 cm 间隔采集4个样品
获得 40 个样品采集后的样品立刻装入干净的聚
乙烯袋内封口保存在 4 的冰库中检测时在常
温下解冻备用
研究区域位置分布示意见图1
涂片鉴定由国家海洋局第二海洋研究所完成
国家地质测试中心进行了沉积物中常量元素
量元素和稀土元素的测定
11涂片鉴定
沉积涂片样品采用涂刮法制作先用洁净
不锈钢针取少许沉积物放于载玻片上加几滴蒸
馏水轻轻涂刮使之均匀分布于载玻片上
然后放入
将加拿大树胶滴在烘干的样
品上盖上盖玻片室温下然干制成固定
在双目镜下对各涂片进行粒度
粉砂
生物和非生
以及沸石和铁锰微结核
等具有特殊成因意义物质的半定量鉴定分析12
12稀土元素检测
物样品在洁净实验室中风干至半干后
放在蒸发皿中于105 的烘箱中烘 2 h 后用研钵研
样品采用氧化钠熔融稀土元素形成氢氧化物
沉淀加三
EDTA 络合钙
稀土元素氢氧化物沉淀溶于 2 mol·L 1
盐酸经强酸性阳离子交换树脂分离富集后再用
5 mol·L 1 盐酸洗提蒸发定容后采用 ICP-MS X-
series测定稀土元素含量
常量元素和其他微量元素的检测方法及测量
精密度见表1
1太平洋研究区域示意图
Fig. 1 Schematic diagram of research area in the Pacific
6 张霄宇等 西太平洋海山区深海软泥中稀土元素富集的地球化学特征 731
1测试项目清单
Table 1 List of measurements
Testing contents Testing methods Testing standards Testing precisionRSD%
Types of sediments Smear identification DZ/ T0223-2001 Qualitative analysis
CO2Carbonate measurement GB9835-1988 0. 70%
Na2OMgOAl2O3SiO2P2O5K2OCaOTiO2MnOFe2O3X-ray fluorescence spectrometer2100GB / T14506.28-1993 <0. 55%
ScCoNiCuZnRbSrZrNbSnBaHfTa Plasma mass spectrometryX-seriesDZ/ T 0223-2001 <5%
LaCePrNdSmEuGdTbDyHoErTmYbLuY Plasma mass spectrometryX-series 5%
本次研究在计算稀土元素含量及特征值时所
采用的计算公式如下
ΣLREE = La + Ce + Pr + Nd + Sm + Eu
ΣHREE = Gd + Tb + Dy + Ho + Er + Tm + Yb + Lu
ΣREE = La + Ce + Pr + Nd + Sm + Eu + Gd + Tb + Dy
+ Ho + Er + Tm + Yb + Lu
LREE / HREE = ΣLREE / ΣHREE
δCe = CeN
Ce*=CeN
LaN+ PrN
2δEu = EuN
Eu*=EuN
SmN+ GdN
2
2数据和结果
涂片鉴定西太平洋海山区和东太
平洋 CC 区沉积物性质差别较大西太平洋海山区
沉积物类型复杂受水深
物质来源等不同因素
麦哲伦海山区钙质软泥分布较广水深较深区
域沉积物主要为含硅质粘土和粘土马绍尔群岛
和莱恩海山的几个站位均发现分布有含沸石粘土
东太平洋沉积物类型简单以硅质粘土为主
不同类型沉积物中稀土元素和其他微量元素含
量差异很大含沸石型深海粘土以富含金属元素为特
而钙质软泥以贫金属元素为特点见图2
对研究区域不同类型沉积物中各个元素以地
壳中的丰度为参照13进行元素的富集程度对比
结果表明 1含沸石深海粘土中常量元素 P2O5
MnOTFe2O3微量元素 ScCoNiCuZnRb
REE Y均为富集ZrNbSnHfTa 则表现为
明显亏损 2钙质软泥中常量元素除了 CaO
度富集其他都表现为严重亏损
微量元素 Sr
度富集Cu Ba 略有富集ScCoNiZnb
表现为亏损ZrNbSnHfTa轻稀土元素 Ce
严重亏损3东太平洋沉积物以硅质沉积为主
元素富集特点和西太平洋海山区粘土质沉积物基本
2太平洋不同类型沉积物中元素富集系数
Fig. 2 Enrichment coefficients of elements from different types of sediments in Pacific
732 31
一致但是富集程度皆明显低于含沸石型深海粘
东太 Ce 负异常程度较低
CaO 极度缺失而区别于西太平洋海山区的硅质沉
4稀土元素在含沸石深海粘土中以极高的含
量和较低的轻重稀土元素比值为特并且 LREE
富集程度 HREECe 是所有稀土元素中富集
程度最低的和该区域 DSDP 站位的数据基本一
7
钙质软泥中稀土元素含量和轻重稀土元素
比值均极低并且随着原子量增加由轻稀土亏损
逐渐表现稀土HREE Dy-LuY
富集系数 1硅质粘土稀土元素含量中
轻重稀土元素比值相对较高东太平洋硅质粘
土中稀土元素含量低于西太平洋海山区同类型的
沉积物
具体见表23
2稀土元素含量分布范围和平均值 μ
g·g-1
Table 2 Ranges and average values of REE content μ
g·g-1
SamplesamountsEigenvalue La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
The abysmal Clay of CC Mean 48.67 87.47 13.44 56.22 13.94 3. 38 14. 38 2.25 13. 47 2. 62 7. 44 1. 05 6 86 1. 03
Area in the Pacific Ocean25Minimum 31.10 66.00 8. 67 36.40 9. 57 2. 22 9. 85 1. 57 9.58 1. 88 5. 27 0. 75 4. 93 0.75
Maximum 74. 70 101. 00 20. 90 89. 10 22. 00 5. 44 22.90 3. 52 21. 00 4.05 11. 40 1. 62 10. 30 1. 56
The calcareous ooze in the west Mean 14.65 12.55 3. 31 14.43 3. 27 0. 78 3. 82 0. 58 3.77 0. 81 2. 38 0. 35 2. 25 0.35
Pacific sea mountains 5Minimum 12. 50 9. 20 2. 65 11. 60 2. 51 0. 61 2. 78 0. 43 2. 78 0. 62 1. 80 0. 25 1. 65 0.25
Maximum 18. 40 21. 40 4. 65 20. 60 4.87 1. 23 5. 84 0. 87 5. 46 1. 15 3. 35 0. 50 3. 17 0.49
The clay in the west Pacific Ocean Mean 61. 97 86. 82 16. 08 67. 57 15. 82 3. 69 16.33 2. 50 15. 22 3.02 8. 69 1. 22 7. 86 1. 18
or siliceous materials 5Minimum 32.50 65.20 8. 30 34.70 8. 34 1. 89 8. 27 1. 28 8. 02 1. 64 4. 65 0. 69 4. 46 0. 68
Maximum 119. 00 131.00 29.50 125. 00 27. 80 6.51 29.40 4. 39 26. 80 5. 34 15. 30 2. 13 13. 50 2. 05
Zeolitic clay in the west Mean 153. 90 116.16 43. 80 188. 78 43. 46 10.14 47.48 7. 20 44. 50 8.92 25. 52 3. 47 22. 02 3. 32
Pacific sea mountains 5Minimum 74. 50 98. 80 22. 00 92. 90 23. 10 5. 38 24.10 3. 62 22. 40 4.33 12. 30 1. 69 10.80 1. 62
Maximum 227. 00 140.00 63.50 275. 00 61. 40 14. 10 69.30 10.40 64. 80 13. 10 37.80 5. 15 32.30 4. 99
3太平洋沉积物稀土元素含量特征值及比较
Table 3 Eigenvalues of REE in Pacific sediments and comparisons with other types of sediments
SamplesamountsEigenval-
ues
REE/
μg·g 1
LREE /
μg·g 1
HREE /
μg·g 1
LREE /
HREE δCe δEu Data
source
Sediments of CC area in Minimum 188. 59 154.01 34. 58 3. 85 0. 51 1. 00 In this research
the east Pacific Ocean25Maximum 386. 49 310. 24 76. 25 5. 13 0. 94 1. 08
Average 272. 22 223. 12 49.09 4. 59 0. 77 1. 05
The calcareous ooze in the west Minimum 188. 59 154.01 34. 58 3. 85 0. 33 0. 85 In this research
Pacific sea mountains5Maximum 2295.15 2101.70 249. 30 11.33 0. 50 1. 01
Average 1143.09 1020. 66 131. 78 7. 48 0. 38 0. 95
The clay in the west Minimum 180. 62 150.93 29. 69 4. 04 0. 48 1. 00 In this research
Pacific sea mountains5Maximum 537. 72 438. 81 98.91 5. 08 0. 86 1. 02
Average 307. 94 251. 94 56.00 4. 60 0. 65 1. 01
The zeolitic clay in the west Minimum 397. 54 316.68 80. 86 3. 28 0. 25 0. 94 In this research
Pacific sea mountains5Maximum 1018.84 781. 00 237. 84 3. 92 0. 53 1. 01
Average 718. 68 556. 24 162. 44 3. 51 0. 34 0. 98
The phosphorite in the west Pacific Ocean Average 286. 88 221. 03 65.85 3. 51 0. 27 0. 98 Zhang F Y et al2011
2
The TAG hydrothermal genesis of crust in the
mid-atlantic ridge6
Average 5. 01 3. 36 1. 65 2. 03 2. 076 1. 03 Mills et al2001
4
The mixed crust in the mid-atlantic ridge2Average 765. 75 649. 82 115. 93 5. 49 0. 669 1. 04
The hydrogenic crust in the mid-atlantic ridge4Average 1948. 74 1765. 56 183.18 9. 65 0. 621 1. 17
Sediments in the Changjiang river14Average 211.10 193.19 17. 91 10. 79 0. 78 1. 09 Yang S Y et al2002
17
Sediments in the Changjiang estuary-the east
China sea shelf
Average 166. 56 148. 91 17.65 8. 44 0. 93 0. 96 Zhang X Y et al2009
18
Sediments in the east of the south China sea106Average 129.44 113.95 15. 50 7. 35 0. 91 0. 99 Zhang X Y et al2012
3
6 张霄宇等 西太平洋海山区深海软泥中稀土元素富集的地球化学特征 733
以上分析表明西太平洋海山区含沸石深海
粘土中稀土元素和其他微量元素含量普遍高于其
他类型沉积REE YCuCoNiBaP2O5
富集含量超过地壳中相应元素丰度的5 10 倍以
重稀土元素含量与我国华南地区广泛分布的
离子吸附型矿床相当14这与 Piper8以及 Kato7
等的研究一致
3
31北美页岩归一化模式
将稀土元素采用北美页岩归一化后表明西太
平洋海山区含沸石深海粘土表现为平缓的北美页岩
模式
中稀土元素略有富集
无明显的倾向性
见图
3
这种平缓型的分布式和 50 μm10以及
以往关于西太平洋海山区深海粘土的研究结论基本
一致
一般认为以陆源物质为主沉积物如长江沉积
东海边缘海大陆架沉积物中轻稀土元素含量较
中稀土元素略有富集北美页岩归一化模式表
现为左倾型15在离陆地较远的边缘海深海海盆如
南海东部深海海盆沉积物中这种明显的左倾模式已
经弱化表明深海沉积作用的加强15而北大西洋
深层水
大西洋洋脊热液结壳
西太平洋海山区钙
质软泥则表现为显著的重稀土富集
轻稀土贫化的
特点为显著的右倾模式太平洋的磷块岩也表现
出一定程度的右倾特征重稀土元素相对富集
成型结壳则表现为平缓型北美页岩模式
3. 2 δCe
研究区域内不同类型的沉积物都具有显著的 Ce
负异常西太平洋海山区含沸石深海粘土则表现出
最为强烈的 Ce 负异常和深海海水
热液结壳
洋深海软泥强烈的 Ce 负异常一致以陆源物质为主
的长江沉积物
长江口东海陆架沉积物以及南海东
部边缘海深海海盆沉积物表现出程度较低的 Ce
异常水成结核现出强烈的 Ce 正异常
一般认为和其他稀土元素不同在近表层环
境下水和沉积物中的 Ce3 + 容易氧化成 Ce4 +
以四价离子存在的稀土元素与相稀土
元素相比相差悬殊的电荷导致 Ce4 + 与其他稀土
元素分离CeOH4Mn
壳的铁相中造成结壳的强烈的 Ce 正异常
水中强烈的 Ce 负异常
中太平洋海山区沉积物富
也为结壳提供了丰富的 Ce因此结壳特别是
水成型结壳以显著的 Ce 正异常为特征
钙质软泥
δCe 则继承了海水的特点表现为显著的 Ce
异常但是其轻重稀土比值高于海15
硅质软泥
3不同沉积类型中稀土元素的北美页岩归一化
Fig. 3 Normalized REE with North American Shale Composite in different types of sediments
1 50 μm phillipsite 2TAG hydrothermal crusts from the Mid-Atlantic Ridge 3TAG heterogenous crusts from the Mid-At-
lantic Ridge 4TAG hydrogenous crusts from the Mid-Atlantic Ridge 5Phosphorite from Western Pacific 6Sediments of
Changjiang River 7Sediments of continental shelf of Eastern China Sea 8Sediments from Eastern South China Sea 9Deep
Sea Water from Northern Atlantic
734 31
的稀土元素特征往往受沉积物中铁锰微结核的影
表现为轻和中稀土元素略微比重稀土元素富
16
陆源河流沉
边缘海东海大陆架浅海
沉积物和南海海盆沉积物的稀土元素分馏特征和
δCe 均继承了中国东部大陆沉积物的特点显示了
其陆源性质具有较高的轻重稀土元素比值和弱
Ce 负异常31718
研究区域沉积物中普遍存在
的中稀土一般认为相比重稀土元
轻稀土元素和中稀土元素更容易被铁锰水合
物结合进而重稀土元素则易于形成
稳定的有机络合物8
由此可见西太平洋海山区含沸石深海粘土
以强烈的 Ce 负异常
平缓的北美页岩归一化模式
以及略微富集的中
重稀土元素为特征3
和磷块岩以及 60 μm沸石的比较接近显示在成
因上可能具有一定的相似性而和体系
中稀土元素的富集机制不同
33REE 和常量元素
通过对海洋沉积物元素组成和含量分析可以
了解沉积物的主要化学成分揭示物质
来源和分抓住划分沉积物类型最本质的
东西19
深海沉积物中常量元素 CaOSiO2以及
Al2O3的含量以及相互之间的比例关系已经被证明
可以用于探讨沉积物的物质来源和成因并且已
经成功地应用于我国南海海盆的深海沉积物分类
与命名1920
一般认为深海沉积物中除了方解磷灰石
也是 Ca 的常见矿物形式其中碳氟磷灰石中 CaO /
P2O5值为 1 621而氟磷灰石中的 CaO / P2O5值为
1. 318Pan 21 CaO / P2O5比值的研究
我国调查区及赤道太平洋的磷酸盐矿物为碳氟磷
灰石而不是氟磷灰石
本次研究对 1. 27CO2/%
+ 1. 621 P2O5/% CaO 的相关性表明钙质软泥
和含沸石型深海沉积物中方解石和碳氟磷灰石应
该可以解释全部的 CaO 存在矿物形式见图 4
对西太平洋海山区不同沉积物类型中 REE
常量元素的相关性表明REE P2O5具有良好的
4 CaO CO2+ P2O5的相关性分析
Fig. 4 Correlation analysis between CaO and CO2+ P2O5
相关性Dubinin 10的研究也表明沉积
50 μm的沸石中 REE 浓度取决于 P含量并认为
可能是沸石中机械混入了同型的含磷矿物Birger
22在澳大利亚浅海砂岩中广泛发育着富含 REE
期成岩磷酸盐矿物但是以轻稀土富集为
特征
REE MnOFe2O3的相关性相对较见图
5常量元素表明该区域可能存在热液来
源的 Fe2O3
23
因此热液铁锰水合物可能也是造
成沉积物中 REE 富集的一个因素
3. 4 REE 和可能的赋存矿物
以往研究表明大洋 REE 的最终输出有两
种主要形式 1REE 包裹型颗粒主要是指表层
吸附了 REE 的粘土矿物和铁/锰水合物 2
物成因的和这两种形式同时沉积的含
REE 自生矿物只占了通量中很少的一部分82425
Piper25认为沸石质深海沉积物富含 REE
可能决定沸石这种可能形成于氧
化环境下火山碎屑物质的海解作用10典型的深海
自生沉积物较低的沉积速率下其含量可达50%
以上体积11因此有理由认为沸石含量对深海
沉积物中 REE 含量有深刻影响计算
到的海洋沉积物 REE 总量远远大于陆源输入量
可能的解释是高估了沸石中的 REE 含量或者是低
估了稀土元素的输入通量Bernat9对太平洋两个
站位的研究表明沸石中轻稀土含量仅为北美页岩
6 张霄宇等 西太平洋海山区深海软泥中稀土元素富集的地球化学特征 735
5稀土元素和常量元素的相关性分析
Fig. 5 Correlation analysis of REE and constant elements
1Calcareous ooze in seamounts areaWestern Pacific 2Deep sea clay in seamounts areaWestern Pacific 3Zeolitic clay in
seamounts areaWestern Pacific 4Deep sea clay in CC zone Eastern Pacific
1 /4 Dubinin 10的研究表明 50 μm
石沉积物中检测到的 REE 不足于解释沉积物中
REE 总量结晶过程中单个沸石晶体中 REE 含量
很低并且强烈的 Ce 正异常与沉积物中完全不
一致
由此可见沸石应该不是沉积物中 REE
集或者载沸石很有可能可以富集磷酸盐
矿物从而导致含沸石型沉积物中 REE 的富集
是显然需要进一步的深入研究
4
1. 东太平洋 CC 区沉积物类型简单以硅质粘
土为主西太平洋海山区分布着类型复杂的深海
沉积物不同类型沉积物中稀土元素和其他微量
元素含量含沸石型深海粘土以富含金
属元素为特点而钙质软泥以贫金属元素为特点
其中 REE YCuCoNiBaP2O5富集
超过地壳中相应元素丰度的5 10 倍以上重稀土
元素含量与我国华南地区广泛分布的离子吸附型
矿床相当
2. 含沸石深海粘土以极高的稀土元素含量和较
低的轻重稀土元素比值为特点主要分布在马绍尔
群岛和莱恩群EE 最高达1018. 84 μg·g 1
其中LREE781 00 μg·g 1 HREE237. 84
μg·g 1 普通深海粘土中稀土元素中等程度富集
而在钙质软泥中则表现为显著的亏损
3. 西太平洋海山区含沸石深海粘土以显著的
Ce 负异常
平缓的北美页岩归一化模式以及略微
富集的中稀和单晶体沸石中 REE
含量和分布模式的差异表明沸石该类
736 31
型沉积物 REE 的主要携带和富集矿物热液铁锰
水合物以及机械混入的含磷矿物等的存在可能对
含沸石深海粘土中 REE 含量有很深刻的影响
4. 含沸石型深海粘土可能和高含量的磷酸盐
有一定相但是其富集作用尚有待于进一步
研究
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Enrichment and Geochemical Characteristics of Rare Earth Elements in
Deep-Sea Mud from Seamount Area of Western Pacific
Zhang Xiaoyu1* Deng Han1Zhang Fuyuan2Zhang Weiyan2Du Yong1Jiang Binbin11. De-
partment of Earth ScienceZhejiang UniversityHangzhou 310027China2 Key Laboratory of
Submarine GeoscienceState Oceanic AdministrationHangzhou 310012China
Abstract40 sediment samples were collected in 18
stations from seamounts areas in Western Pacific and
from CC zone in Central Pacific. Based on the meas-
urements of main elements and minor elements inclu-
ding Rare Earth Elements REEs the geochemical
characteristics of REE enrichment in zeolitic clay were
analyzed. The zeolitic clay was found to be distributed
mainly at Marshall Seamounts and Line Islands
marked by high content of metal elements and espe-
cially of REEs. The observed highest content of REE
in zeolitic clay was 1018 84 μg·g 1 with the highest
LREE of 781 00 μg·g 1 and the highest HREE
of 237 84 μg·g 1 which were comparable to or even
greater than REEs content from the southern China
ion-absorption-type deposits. The normalizd REEs
with North American Shale Composite NASCin ze-
olitic clay displayed gentle slopedistinct negative Ce
anomaly and fractionation of HREE and LREEwhich
suggested that combined effect of hydrothermally Fe-
Mn oxyhydroxides and mixture of phosphatic mineral
formed during early diagenesis are possible mechanism
of REEs enrichment in zeolitic claybut needs further
study.
Key wordsseamounts areas in Western Pacificzeolitic clayenrichment characteristicsrare earths
... More than 6500 ppm REY in sediments was later found in the Minami-Torishima area in the Western Pacific [4] . High REY contents in zeolite clays have also been reported in the eastern Pacific [6] , in seamount areas of the western Pacific [7] , in the central Pacific [8] , and in the Clarion-Clipperton region (CC zones) of the eastern Pacific [9] . In addition, the DSDP site 213 from the eastern Indian Ocean has proven to be a zeolite clay of elevated REY contents with negative Ce anomalies [5] . ...
... However, low REY contents in phillipsite have challenged this opinion [4,11,12] . Dubinin et al. [12] suggested that the mixture of fossil fish debris and Fe-Mn oxyhydroxide during the development of phillipsite contributes primarily to the co-existence of phillipsite and high REY contents, which is in agreement with other researchers [7,8] . Fossil debris bio-apatite was proposed to be the main host of REY for decades [11,[13][14][15][16] . ...
... Overall, the samples are characterized with a distinct [5] ; Site 170 [3] ; WP: West Pacific [7] ; CCZ: Clarion and Clipperton Fracture Zones [51] . All of the above are zeolite clays) loss of LREE and enrichment of HREE, very strong negative Ce anomalies, slight positive Eu anomalies, and strong positive Y anomalies, which is similar to REY rich zeolite clay and apatite collected from the Pacific Ocean [3,4] . ...
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... Utilizing the characteristics of sub-bottom profiles to distinguish the types of deep-sea sediments is of great significance in the investi of REY-rich deep-sea sediments. Recent surveys and studies have shown that REEs are primarily present in Pacific pelagic clays and zeolite clay sedimentary layers [24][25][26][27][28][29][30][31]. Wang Haifeng et al. [21] have proposed that the transparent layer, distinguished by its acoustic properties, can serve as the target horizon for the REY-rich sediment layer. ...
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Concentrations and compositions of rare earth elements (REE) in three micronodule fractions (50–250, 250–500, and >500 µm), coexisting macronodules, and host sediments are examined. The samples were collected from three sites (Guatemala Basin, Peru Basin, and northern equatorial Pacific) located in elevated bioproductivity zones of the surficial water. The influence of micronodule size is dominant for REE compositions and subordinate for REE concentrations. For example, the Ce concentration inversely correlates with the micronodule fraction dimension and drops to the lowest value in macronodules and host sediments. The Ce decrease is generally accompanied by the Mn/Fe increase in micro- and macronodules. Hence, the role of diagenetic source of material directly correlates with the micronodule dimension. The contribution of diagenetic source is maximal for macronodules. The REE signature distinctions of micronodules and macronodules can be attributed to variations of hydrogenic iron oxyhydroxides and diagenetic (hydrothermal) iron hydroxophosphates that are the major REE carriers in ferromanganese ore deposits. The relationship and general trend in the chemistry of coexisting macronodules suggest that they can represent products of the initial stage of nodule formation.
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Composition of REE in the surface sediment of continental shelf around Changjiang River Estuary suggested that the sediments were mainly from continental source. The grain size and CI content were not main factors controlling fractionation of REE. The LREE/HREE was a promising index distinguishing sediments from Changjiang and Huanghe drainage basins. The erosive sediment of old Huanghe Delta transported by southern Yellow Sea coastal current had low LREE/HREE. The sediment carried by Changjiang River had relatively high LREE/HREE. The source rock and two unique weathering regime of Chanjiang and Huanghe drainage basins were key factors causing fractionation of REE in sediment. With hierarchical cluster analysis, the research area was classified as two areas. One was Changjiang Estuary area, where the element composition corresponded well with that of Changjiang sediments. The other was continental shelf of northern East China Sea area, where the element composition was in accordance with that of Huanghe sediments.
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Scientific classification of the geological objects is one of the most important basic research topics in geology. In this paper, thorough review of current research situation is made to establish the classification and nomenclature of deep sea sediments which unify the quantification and can be easily operated. Researches on various topics were conducted, eg., the composition and distribution of oceanic sediments, the relationship between water depth, average grain size and clay content, the discrepancy of clay, calcareous and siliceous content determination between smear and chemical analysis. The authors establish the quantitative relationship between calcareous and CaCO 3, between siliceous and biogenic SiO 2. This paper also compares and calibrates sedimentation method and laser method for grain size determination, and discusses generality and comparability of the classification and nomenclature system. Innovative key technique and scheme of classification and nomenclature for deep sea sediments were then put forward. The deep sea sediments are classified as deep sea clay, calcareous ooze, siliceous ooze, and clay-siliceous-calcareous ooze according to the simple classification method. The simple classification satisfies the general requirement of marine geological survey and basic understanding of sediment types. This method considers existing sediments mixture and existing classification methods. The deep sea sediments are further classified into 16 sub-types based on the sophisticated classification method, which therefore gives more detailed and comprehensive descriptions for the deep sea sediments and satisfies the requirement for comprehensive marine investigation. The classification and nomenclature for deep sea sediments are comparable with that for shallow sea sediments on diagram, indices, amount of types, naming methods, representation of mixture sediments and operability. Therefore, the classification and nomenclature for deep sea sediments is designed to be a succession of shallow sea sediments classification.
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The relative and absolute concentrations of rare earth elements (REE) in authigenic and biogenic phases of deep-sea sediments are quite different. Competition between these phases for REE has resulted in fractionation from the parent material, the latter consisting predominantly of terrigenous material, but with a contribution from marine volcanism. The strongest feature of this fractionation is a depletion of Ce, relative to La, in CaCO3, opalline silica, phillipsite, phosphorite, barite, and montmorillonitic clays; and a Ce enrichment in Fe/Mn nodules. The distribution of REE in different masses of seawater strongly reflects their fractionation in sediments. Whereas the relative concentration of REE in rivers resembles that of shale, their removal from seawater by authigenic and biogenic phases results in: (1) a decrease of their total concentration; (2) a depletion of Ce; and (3) an enrichment of heavy REE relative to light REE. The order of fractionation for water masses in the Atlantic Ocean is:Antarctic intermediate water > North Atlantic deep water > Antarctic bottom water> shelf water > river water ∼ shale.The shale-normalized pattern for the sum of REE in the authigenic and biogenic phases of pelagic sediment and in seawater resembles that of an admixture of shale and basalt corresponding presumably to the realtive inputs from continents and marine volcanism respectively. The estimated rate of accumulation of each REE in the sediment, however, is approximately 12 times the estimated rate of input of REE from these two sources.
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RARE earth element (REE) patterns of Upper Jurassic, Kimmeridgian, shales from various localities are shown here to have only minor variation in spite of deriving from very different source rocks. The formation of such uniform patterns indicate that these sediments are mature, well mixed and formed in similar depositional environments. An extension of the North Sea Kimmeridgian petroleum source rocks is indicated. Minor differences in REE patterns can be related to variations in the sand/silt content.
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The concentrations of rare-earth elements (REE) have been measured in 31 ferromanganese nodules from the Pacific and Indian Oceans and vary by almost a factor of 5. Too few nodules have been analyzed to define possible regional trends. The shale-normalized patterns, however, permit division of nodules into two groups: those from depth greater than 3000–3500 m and those from less depth. The factors that determine this change in the relative concentration of REE may be related to the mineralogy of manganese phases and/or the transport of REE to the deep ocean by particulate matter.Comparison of the REE patterns of nodules with those of phillipsite, phosphorite, clays, CaCO3 and seawater suggests that the patterns of these phases reflect fractionation from an initial pattern closely resembling that of shale. By assuming that the accumulation rate of REE in clays, CaCO3 and nodules is represented by that for surface sediments, it has been possible to estimate an accumulation rate of phillipsite in pelagic sediments of the Pacific of 0.02 mg/cm2/yr.
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This paper focuses on two of the largest rivers and estuaries of Papua New Guinea (PNG), the Fly and Sepik and explores the degree to which river input and estuarine reactions affect the rare earth element (REE) composition of surface sea water in the western tropical Pacific Ocean. The dissolved phases of the Fly and Sepik River waters have striking REE compositions in the form of large MREE-enrichments as defined by a gradual increase in their shale normalized ratios toward the middle of the REE series. This river/weathering signature is quite distinct from the REE composition of Pacific Ocean sea water. Large scale removal of dissolved river REE occurs in the low salinity regions of the Fly and Sepik River estuaries due to the coagulation of Fe-humic colloids. Laboratory experiments show that the reaction of Fly River particles with sea water leads to the preferential release of MREE to estuarine waters. Additional experiments suggest that the development of MREE-enrichments in PNG rivers is associated with phosphate minerals and their aquatic chemistry. The development of MREE-enrichments in the Fly and Sepik Rivers, through the combination of weathering and estuarine reactions, provides what is termed an island weathering signature to the ocean waters of the western tropical Pacific Ocean. MREE-enrichments appear in the high salinity estuarine waters surrounding PNG and in the subsurface waters of the equatorial (150°E) Pacific Ocean north of PNG (station SA-5 of Zhang and Nozaki [Zhang, J., Nozaki, Y., 1996. Rare earth elements and yttrium in seawater: ICP-MS determinations in the East Caroline, Coral Sea, and South Fiji basins of the western South Pacific Ocean. Geochim. Cosmochim. Acta 60, 4631–4644.]). We interpret MREE-enrichments in the Pacific Equatorial Undercurrent (P-EUC) at SA-5 to reflect the entrainment of an island weathering signature by the regional currents. The REE data in this paper support, but do not conclusively confirm, the proposition of Gordon et al. [Gordon, R.M., Coale, K.H., Johnson, K.S., 1997. Iron distributions in the equatorial Pacific: implications for new production. Limnol. Oceanogr. 42, 419–431.] that there is transport of Fe and other lithogenic elements across the Pacific Ocean within the Equatorial Undercurrent. While they suggested volcanism and hydrothermal activity in the region of PNG to be the source of the lithogenic elements, we favour the hypothesis of Milliman et al. [Milliman, J.D., Farnsworth, K.L., Albertin, C.S., 1999. Flux and fate of fluvial sediments leaving large islands in the East Indies. J. Sea Res. 41, 97–107.] that the massive weathering of islands in the East Indies is a quantitatively more important source. This process involves the entrainment of dissolved and particulate matter from island rivers into the Bismarck Archipelago Undercurrents, which originate in the Coral Sea and move to the P-EUC through the Solomon and Bismarck Seas. Specifically, our REE data are consistent with hydrographical and sedimentological studies which show that the rivers on New Guinea's north coast directly inject their dissolved and particulate matter into the New Guinea Coastal Undercurrent (NGCU), which feeds the Equatorial Undercurrent.
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The rare earth element (REE) geochemistry of various phases from the active TAG hydrothermal mound has been examined and related to their mineralogy and fluid chemistry. The mound deposits range from black and white smoker chimneys, massive anhydrite/sulphide mixtures, oxides, and ochres. All phases, except black smoker chimney anhydrite, demonstrate a positive Eu anomaly when normalised to chondrite REE values. REE substitution into sulphide and sulphate phases appears to be strongly influenced by crystallographic control for all REE other than Eu. Precipitation of anhydrite within the TAG mound is the major mechanism for removal of REE during mound circulation and 0.15-0.35 g anhydrite is inferred to precipitate from every kg of fluid venting from the white smoker chimneys. Oxides from the mound fall into three different categories with distinct REE patterns: oxide rims on sulphides, atacamite-bearing oxides, and silica-rich Fe-oxides and ochres. The oxide rim phases contain sulphide and seawater derived REEs whereas the atacamite-bearing oxides and the ochreous material exhibit no seawater signature which suggests precipitation from, or alteration by, a modified hydrothermal fluid.
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Rare earth element (REE) measurements were carried out on samples from black- and white-smoker vents from the TAG and Snakepit sites at 26° and 23°N on the Mid-Atlantic Ridge. Fluids are substantially enriched in REEs over seawater, by factors of 102 in light-REEs, 103 in Eu, and 101 in heavy-REEs. White-smoker REE patterns appear to reflect the effects of shallow subsurface flow. Samples collected from within 0.5 m above the throats of vents (up to ∼ 10 times dilution) indicate that the REEs behave in a conservative fashion with no evidence of removal at this stage of plume evolution. Higher in the buoyant plume (40–100 m above the vent orifice) where entrainment ratios of seawater to vent fluids are ∼100–700, dissolved REEs fall below the dissolved ambient seawater levels (e.g. seawater: Nd = 21.4 pmol kg−1, Ce = 5.44 pmol kg−, Eu = 1.06 pmol kg−1, Er = 5.47 pmol kg−1; plume waters: Nd = 1.22 pmol kg−1, Ce = 1.12 pmol kg−1, Eu = 0.35 pmol kg−1, Er = 0.45 pmol kg−1). The dissolved REE pool shows a net shortfall of 90–98% but the total REEs fall on conservative mixing lines because of REE uptake by plume particulates. REE/Fe ratios in buoyant plume particles are consistent with a kinetic model for Fe2+ oxidation and coprecipitation of REEs with Fe oxides. The trend in the REE/Fe ratios of the particles indicate that in addition to initial coprecipitation and uptake, scavenging of REEs must occur during dispersion of the particles through the neutral plume. The results of the study demonstrate that scavenging processes, by precipitating Fe-oxyhydroxides, eliminate the impact on seawater of the enrichments of REEs from hydrothermal fluids such that the seawater experiences a net depletion of REEs as a consequence of hydrothermal activity.