中西太平洋海山富钴结壳中稀土元素分布特征

<正>中西太平洋海山是富钴结壳广泛分布的区域,大量文献报道了该区域富钴结壳中稀土元素特征。富钴结壳中稀土元素含量受控因素较多,其中磷酸盐化作用是影响富钴结壳中稀土元素含量的重要因素之一(王吉中,2005)。稀土元素Ce、REE3+和Y在富钴结壳中富集特征也不同。因此,未对富钴结壳及稀土元素进行分类,而简单的对其稀土元素总量取平均值进行比较,很难准确地反映不同海区内富钴结壳中稀土元素的     

西太平洋海山富钴结壳稀土元素(REE)组成原位LA-ICPMS测定

利用激光剥蚀电感耦合等离子体质谱(LA-ICPMS)微区原位分析方法,对采自西太平洋海山具完整三层结构的富钴结壳样品进行了稀土元素(REE)含量测定,结果表明, 虽然均产于西太平洋海山且均具有明显的三层结构,富钴结壳化学组成受地理位置和沉积环境影响很大。绝大多数西太平洋富钴结壳具有高ΣREE、高LREE/HREE、δCe正异常和δEu基本无异常或微弱正异常的特点, 显示它们主要由正常海水沉积形成。结壳不同层圈之间REE组成有较大的区别, 其原因主要在于其形成环境和矿物组成不同。样品0327稀土元素总量(∑REE)由亮煤层到疏松层到外层逐渐升高,且亮煤层δCe和Y/Ho变化非常大,最大值分别为38.61和105.5,显示该层生长环境较为氧化且相对动荡,而样品0346中三层结构的∑REE都非常高,且变化趋势与0327正好相反,从亮煤层到致密层∑REE有降低的趋势。 亮煤层形成时海水相对较氧化的环境有利于铁锰氧化物的形成和Ce⁴⁺等稀土元素的吸附,导致其中ΣREE较疏松层和外层为高,而后期磷酸盐化导致REE元素的迁移和亏损。在结壳生长剖面上,由最外层到疏松层和亮煤层,δCe呈明显上升趋势,且变化范围趋大,说明该结壳所处的海水环境在由老至新的生长过程中由相对动荡和氧化变为相对平静和还原。     

中太平洋WM1和WX海山富钴结壳元素相关性及其层间变化研究

在结壳矿物学等基本特征分析的基础上,对中太平洋WM1和WX海山富钴结壳中的主量元素、微量元素、稀土元素和铂族元素含量、层间变化及其相关性进行了研究,结果表明:本区结壳从下层到上层,粘土矿物和石英等碎屑矿物逐渐增多,很可能与青藏高原的隆升和剥蚀以及亚洲季风演化有关;TFe/Fe2 从结壳下层到上层逐渐增高,反映了结壳的氧化性由下层到上层增强,海山的沉降可能是造成结壳生长后期环境氧化性增强的重要原因;Ti、Co、Pb、As、Mn、TFe等元素与TFe/Fe2 呈正相关,反映结壳中这些元素的富集与氧化环境有关,而Ca、P、Pt和∑REE等元素与TFe/Fe2 呈负相关,反映结壳中这些元素的富集与还原环境有关;Fe与Co显著正相关是本区结壳的重要特点;结壳的Co与(Fe Mn)的相关性大于Co与Fe的相关性及Co与Mn的相关性;P含量小于1%时,Co与P相关性不明显,当P含量大于1%时,Co与P呈明显负相关,磷酸盐化的过程对铁锰结壳吸附Co的能力起到抑制作用。聚类分析将Pt、∑REE与P和Ca分为一组,说明在结壳中Pt和∑REE主要赋存在碳氟磷灰石中,结壳的磷酸盐化的过程对Pt和∑REE的富集起到了重要的作用。     

铁锰结壳中底层洋流活动的地球化学研究

文章以大洋海山铁锰结壳与南极底层流(AABW)之间关系的角度,从铁锰结壳的结构构造、矿物组合,特别是结壳新壳层的Ce异常和Ce/La比值的区域分布来探讨AABW的活动在铁锰结壳中留下的证据。主要对中太平洋和西北太平洋5座海山的17个铁锰结壳新壳层样品进行了结构构造分析和REE含量测定。结果表明,铁锰结壳的REE含量很高,平均为1716.66×10-6,且轻稀土元素明显富集,LREE/HREE平均值为4.82,除MID06样品具微弱的Ce负异常外,其他铁锰结壳样品均具明显的Ce正异常。为了对比研究AABW的影响,除铁锰结壳外,还引用了不同区域的多金属结核的稀土元素平均值资料按不同区域进行了对比研究,结果发现,AABW活动区和非活动区的δCe值和Ce/La比值有显著差异。一般来说,沿AABW流路,从南向北,δCe值和Ce/La比值有逐渐减小的趋势,但在局部地区,如地形复杂的海山区,AABW的强度会发生变化,其Ce正异常和Ce/La比值可能会局部增大。本项研究成果将有助于全面认识大洋成矿作用与海洋环境变迁的内在联系。     

麦哲伦海山群MK海山富钴结壳稀土元素的赋存相态

利用ICP-OES和ICP-MS,分析了麦哲伦海山群西北端MK海山2 170 m水深的MKD23B-3号富钴结壳样品,获得了其剖面上主元素、稀土元素（REE）和Y含量数据,并基于元素含量间的线性相关关系,研究了REE和Y的赋存相态。结果显示:该样品剖面从基岩到表面可划分为5层,第Ⅰ、Ⅱ层为磷酸盐化壳层,第Ⅲ、Ⅳ、Ⅴ层为未磷酸盐化壳层。在未磷酸盐化壳层中,REE和Y主要赋存在δ-MnO₂相中;而在磷酸盐化壳层中,REE和Y除了赋存在Fe、Mn氧化物相中外,主要赋存在独立于碳氟磷灰石（CFA）的矿物相态中,可能为稀土的磷酸盐。并提出利用磷酸盐中REE/Y 估算富钴结壳磷酸盐化壳层次生稀土的方法,据此估算了MK海山富钴结壳磷酸盐化壳层次生稀土的量。在该样品中,次生稀土占稀土总量的42%~88%,近一半以上的稀土是次生的,磷酸盐化作用对于REE和Y的次生富集具有显著的贡献;因此解读磷酸盐化富钴结壳的稀土元素（特别是Nd同位素）古海洋记录必须排除次生稀土元素的干扰。     

大洋锰结核(壳)中南极底流活动的矿物学与地球化学记录

总结了大洋锰结核(壳)的形态、构造、矿物组合、元素富集特点,以及区域分布和南极底流活动的关系,采用ICP-MS测试手段对中太平洋海山区17个锰结壳样品和1个基岩样品的稀土元素进行测试,结果表明,富钴结壳的REE含量很高,平均为1716.66×10-6,轻稀土明显富集,LREE/HREE平均为4.82,锰结壳样品中除MID06样品有轻微的Ce负异常外,其余样品均具明显的Ce正异常,基岩MKD01呈明显的Ce负异常。不同区域锰结核(壳)中稀土元素的对比研究表明,南极底流活动区和非活动区Ce/La值有显著差异,但不能通过Ce/La值确定底流的迁移路径。这一成果将有助于全面认识大洋成矿作用与海洋环境变迁的内在联系。     

海水Ce含量对赤道印度洋和西北太平洋富钴结壳Ce富集的制约

富钴结壳是一种潜在的多金属资源,富含Co、REEs、Pt、Te等。其中,Ce的含量特别高,具有较高的经济价值,研究其富集的控矿要素具有重要意义。Takahashi等(2007)认为富钴结壳中Ce的富集是一个动力学过程,富钴结壳生长速度是关键因素。赤道印度洋和西北太平洋富钴结壳的生长速率分别为2.48mm/a和1.78mm/a,尽管其生长速率差别不大,但是其Ce含量却有     

东菲律宾海新型铁锰结壳中元素的赋存状态

为了解东菲律宾海新型铁锰结壳中元素的赋存状态, 采用化学提取方法对3个结壳样品进行了物相分析.不同类型结壳中成矿和稀土元素的赋存状态总体一致, 表明它们形成于相近的地质和海洋环境中.成矿元素中的Fe和Cu绝大部分赋存在残渣态中, Mn、Co和Ni则主要赋存在锰氧化物结合态、有机结合态和残渣态中, 并且埋藏型结壳样品锰氧化物结合态中赋存了相对更高比例的成矿元素.三价稀土元素主要集中在锰氧化物结合态中.两个沉积物表层结壳样品中的Ce主要集中在残渣态中.而埋藏型结壳样品中的Ce则主要赋存在锰氧化物结合态中, 这可能与该样品此相态中赋存了相对较多的Mn有关.呈碳酸盐结合态和有机结合态的稀土元素含量仅各占稀土总量的1%左右, 表明两者对结壳中稀土元素的富集作用很小.      

太平洋库克群岛结核结壳稀土成矿研究

太平洋海底蕴藏着丰富的矿产资源。事实表明,稀土不仅蕴含于深海软泥中,还蕴含于海底多金属结核和富钴结壳,而且两者的平均稀土含量高于深海软泥。本文统计并计算了世界上公开发表的富钴结壳和多金属锰结核的稀土数据。结果表明,全球多金属锰结核的稀土元素和钇REY平均含量为1000 μg/g,重稀土和钇(HEY)在结核结壳中的比重则普遍高于15%;而富钴结壳中的REY平均含量则为2310 μg/g,远高于多金属锰结核的稀土含量。     

中太平洋YJC海山富钴结壳矿物组成与元素地球化学

运用等离子光谱、等离子质谱、X射线衍射、红外光谱和场发射电镜等分析测试方法,对太平洋威克(Wake)海岭YJC海山中的富钴结壳中不同构造层的矿物组成和元素地球化学研究表明:矿石矿物是水羟锰矿和少量的钙锰矿,脉石矿物是磷灰石、石英和方解石等,微量矿物有蒙脱石、高岭石、钠沸石、斜发沸石、伊利石、水黑云母、磁铁矿和角闪石等。老结壳磷灰石的质量分数>10%,P>1%;新结壳磷灰石<10%,P<1%。老结壳相对富集Cu、Ca、P等元素,新结壳相对富集TMn、TFe、Co、Ni、Ba、Zn、Pb、Mo等元素。结壳内部纹层构造的不同位置及包体内的微区成分变化较大,TMn和TFe呈同消长关系,但TMn/TFe值相对稳定。结壳的稀土元素总量为1761.88×10-6,Ce具明显的正异常。老结壳相对富集稀土元素,新结壳略富Eu。     

Rare Earth Elements Composition and Constraint on the Genesis of the Polymetallic Crusts and Nodules in the South China Sea

The rare earth elements(REE) composition of the polymetallic crusts and nodules obtained from the South China Sea(SCS) were analyzed through inductively coupled plasma mass spectrometry.Results revealed great differences in the REE abundances(∑REE) of the SCS polymetallic crusts and nodules; the crusts show the highest ∑REE, whereas the nodules exhibit the lowest ∑REE. The similarity in their NASC-normalized patterns, the enriched light REE(LREE), the markedly positive Ce anomaly(δCe), and the non-or weakly positive Eu anomaly(δEu), suggest that the polymetallic crusts and nodules are of hydrogenetic origin. Moreover, the REE contents and their relevant parameters are quite different among the various layers of the crusts and nodules, which probably results from the different marginal sea environments and mineral assemblages of the samples. The growth profiles of the SCS polymetallic crusts and nodules reveal the tendency ∑REE and δCe to slightly increase from the outer to the inner layers, suggesting that the growth environments of these samples changed smoothly from an oxidizing to a relatively reducing environment; in addition, the crust ST1 may have experienced a regressive event(sea-level change) during its growth, although the REE composition of the seawater remained relatively stable. On the basis of the regional ∑REE distribution in the SCS crusts and nodules,the samples collected near the northern margin were influenced by terrigenous material more strongly compared with the other samples, and the REE contents are relatively low. Therefore, the special geotectonic environment is a significant factor influencing the abundance of elements, including REE and other trace elements. Compared with the oceanic seamount crusts and deep-sea nodules from other oceans,the SCS polymetallic crusts and nodules exhibit special REE compositions and shale-normalized patterns, implying that the samples are of marginal sea-type Fe-Mn sedimentary deposits, which are strongly affected by the epicontinental environment, and that they grew in a more oxidative seawater environment. This analysis indicates that the oxidized seawater environment and the special nano property of their Fe-Mn minerals enrich the REE adsorption.     

Rare earth elements and strontium isotopes of polymetallic nodules from southeastern Pacific Ocean

Rare earth element (REE) distributions and ⁸⁷Sr/⁸⁶Sr ratios were determined for nodule crusts and associated surface sediments collected in the southeastern Pacific Ocean between South America and the Tuamotu archipelago. The shale-normalized patterns of the REE from the surface sediments show pronounced negative anomalies in Ce which indicate a marine origin. One ⁸⁷Sr/⁸⁶Sr ratio also has a value characteristic for seawater strontium. REE patterns from the nodule crusts, when normalized to shales, seawater or associated surface sediment, show that a marine origin can also be proposed for the oxy-hydroxides. Only the Ce shows a systematic scatter, which could be the result of fluctuations in the oxidation-reduction conditions during nodule growth. The marine origin for REE is corroborated by the ⁸⁷Sr/⁸⁶Sr ratios which average 0 · 70905 ± 0 · 00019 (2σ), a value close to the seawater ⁸⁷Sr/⁸⁶Sr ratio of 0·70910 ± 0 · 00035. If the major metals of the polymetallic nodules have the same origin as these trace elements, then a direct precipitation from seawater can be postulated for the crusts studied here.     

南海东部次海盆海山链多金属结核(壳)地球化学特征及成因

为了进一步解释南海不同区域内多金属结核（壳）的地球化学特征与成因,对东部次海盆黄岩?珍贝海山链上新获取的多金属结核（壳）样品进行了X光衍射、X荧光光谱测试、SEM-EDS分析和X Series2 ICP-MS测试,详细分析了样品的矿物组成、地球化学成分特征. 结果表明,矿物组成为水羟锰矿、石英、斜长石等;主要造岩元素中Si、Al含量较高,与陆缘碎屑物影响较大有关;富含Mn、Fe、Co、Ti、Ni、Pb、Sr等多种金属元素,相比南海其他区域,具有中等的Fe、Mn含量特征,地化元素特征与南海西北陆坡发现的铁锰结核（壳）相似;稀土元素具有总量高（平均2 070.01×10-6）的特点,高于南海北部其他样品,与西太平洋结壳稀土含量接近（接近工业品位）,指示了重要的稀土资源前景. 结核Be同位素结果指示该区铁锰结核生长时代为1.17~8.51 Ma,形成于晚中新世大量火山喷发之后,因此水成作用是南海东部次海盆海山链结核（壳）的主要控制作用,而陆源物质的输入、火山作用和高压富氢离子海水的浸取作用都为结核（壳）的形成提供了有利的沉积环境.      

Rare earth element geochemistry of oceanic ferromanganese nodules and associated sediments

Analyses have been made of REE contents of a well-characterized suite of deep-sea (> 4000 m.) principally todorokite-bearing ferromanganese nodules and associated sediments from the Pacific Ocean. REE in nodules and their sediments are closely related: nodules with the largest positive Ce anomalies are found on sediments with the smallest negative Ce anomalies; in contrast, nodules with the highest contents of other rare earths (3 + REE) are found on sediments with the lowest 3 + REE contents and vice versa. ${}^{143}\text{Nd}{}^{144}\text{Nd}$ ratios in the nodules (～0.51244) point to an original seawater source but an identical ratio for sediments in combination with the REE patterns suggests that diagenetic reactions may transfer elements into the nodules. Analysis of biogenic phases shows that the direct contribution of plankton and carbonate and siliceous skeletal materials to REE contents of nodules and sediments is negligible. Inter-element relationships and leaching tests suggest that REE contents are controlled by a P-rich phase with a REE pattern similar to that for biogenous apatite and an Fe-rich phase with a pattern the mirror image of that for sea water. It is proposed that 3 + REE concentrations are controlled by the surface chemistry of these phases during diagenetic reactions which vary with sediment accumulation rate. Processes which favour the enrichment of transition metals in equatorial Pacific nodules favour the depletion of 3 + REE in nodules and enrichment of 3 + REE in associated sediments. In contrast, Ce appears to be added both to nodules and sediments directly from seawater and is not involved in diagenetic reactions.     

西太平洋海山富钴结壳的稀土和铂族元素特征及其意义

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.      

Rare Earth Elements in Manganese Nodules from the Central Pacific Ocean

Manganese nodules in areas CP and CC of the central Pacific are rich in REE. Comparatively speaking,the REE contents of nodules in area CP are hihger than those in area CC; and the REE contents of nodulesfrom seamounts are higher than those of nodules from sea-floor plains and hills. Within the nodules, the REEshow a zonal distribution. The REE distribution patterns of the nodules are similar to those of the sedimentsand have a mirror image relationship with those of the sea water. Trivalent REE were not obviously differenti-ated when they entered into the nodules from the sea water.A major factor causing the difference of REE abundances between nodules and sediments is the redoxconditions. The redox intensity of the ocean floor of the Pacific is controlled mainly by Antarctic Bottom Wat-er(AABW), The iron-bearing facies in the nodules is the main carrier of REE.     

等离子体发射光谱法同时测定大洋富钴结壳中硅锰铁钙镁铝钛

大洋富钴结壳试样经ＨＣｌ＋ＨＮＯ３＋ＨＦ溶解,在０．２ｍｏｌ／ＬＨＦ和０．１３ｍｏｌ／ＬＨ３ＢＯ３介质中,用感耦等离子发射光谱法同时测定Ｓｉ、Ｍｎ、Ｆｅ、Ｃａ、Ｍｇ、Ａｌ、Ｔｉ元素的含量。方法经国家标准物质ＧＢＷ０７２４９大洋多金属结核验证,其结果与标准值相符,精密度ＲＳＤ〈３．２％（ｎ＝６）;已应用于太平洋富钴结壳中多元素分析。     

中太平洋YJB海山富钴结核矿物组成与元素地球化学

研究样品采自马尔库斯（MARCUS）海脊YJB海山。利用等离子光谱、等离子质谱、X射线衍射、红外光谱、场发射电镜等分析测试方法,对其富钴结核中不同构造层的矿物组成和元素地球化学研究表明： 该球状结核核部是玄武岩,向外具四层构造。矿石矿物为水羟锰矿和少量的钙锰矿,脉石矿物为磷灰石、石英、斜长石等,微量矿物有蒙脱石、高岭石、钠沸石、方英石、辉石、束沸石等。老结核相对富TMn、Cu、Ca、P等元素,新结核相对富集TFe、Co、Ni、Si、Al等元素。在老、新结核中,从下部构造层到上部构造层,TMn、Co、Ni、Cu、Ba、Zn、Pb、Mo等的质量分数逐渐减少,TFe逐渐增加。核内玄武岩属大洋板内玄武岩,其成因可能与地幔柱有关。结核的稀土元素总量是1 924.07×10^-6,Ce具明显的正异常。在老、新结核不同构造层中,Ce的演化趋势同TMn等元素,其他稀土元素与Fe等相似。     

Comparison of elemental accumulation rates between ferromanganese deposits and sediments in the South Pacific Ocean

Rates of accumulation of Fe and Mn, as well as Cu, Ni, Co, Pb, Zn, Hg, U and Th have been determined for five ferromanganese deposits from four localities in the South Pacific Ocean.Manganese is accumulating in nodules and crusts at a rate roughly equivalent to that found to be accumulating in sediments in the same area. Iron shows a deficiency in accumulation in nodules and crusts with respect to sediments, especially near the continents, but also in the central and south-central Pacific. Copper is accumulating in nodules and crusts at a rate one order of magnitude less than the surrounding sediments.This is interpreted as meaning that most of the Mn is supplied as an authigenic phase to both sediments and nodules while Fe is supplied mostly by ferromanganese micro-nodules and by detrital and adsorbed components of sediments; and Cu is enriched in sediments relative to nodules and crusts most probably through biological activity.