北冰洋门捷列夫海岭富锰棕色层稀土元素组成特征与来源初步分析

北冰洋深海广泛分布的富锰棕色沉积层(棕色层)是海冰、洋流、物源供给等多种因素共同作用的结果，本文基于西北冰洋门捷列夫海岭ARC07-E25岩芯沉积物稀土元素与微量元素含量、颜色反射率参数、粗颗粒组分和无机碳含量的变化特征，对该类沉积层中稀土元素的组成特征、形成机制和物质来源进行了综合分析。结果显示，沉积物稀土元素总含量(∑REE)在122.37×10?6～231.94×10?6之间变化，北美页岩标准化配分模式显示出轻微的中稀土(MREE)富集以及由La、Ce、Nd主导的较强的轻稀土(LREE)优势。沉积物中∑REE随着粗组分颗粒(如冰筏碎屑)的增多而呈现降低趋势，表明门捷列夫海脊沉积物中的稀土元素主要富集在细粒沉积物中。根据∑REE在沉积物中的变化特征将E25岩芯沉积物划分为4种地层，反映出了冰期/间冰期的气候转变过程中温暖条件下形成的棕色层与寒冷条件下形成的浅灰绿色沉积层(灰色层)的岩性旋回中稀土元素组成的差异，由于两种沉积层在形成时受到不同的底层水氧化还原环境的控制，导致了铈(Ce)元素在氧化水体中会由Ce3+氧化为Ce4+并发生沉降，而在还原水体中则由Ce4+还原为Ce3+发生溶解，这一特性使LREE含量产生较大波动，进而影响到∑REE，使之趋于在代表氧化条件的棕色层中升高而在代表还原条件的灰色层中降低。R型因子分析和物质来源判别结果显示，E25岩芯沉积物中稀土元素与亲碎屑元素(Nb、U、Th)有较好的相关性，主要来源于东西伯利亚海和新西伯利亚群岛的近岸侵蚀物质以及勒拿河物质的输入。     

稀土元素在成岩型海洋铁锰结核中的富集特征及机制

借助相分析中的偏提取方法对取自东太平洋深海平原上的成岩型铁锰结核进行了选择性提取实验以研究稀土元素在其中各矿物或氧化物相中的分布模式以及铁氧化物和锰氧化物对稀土元素的吸附机制.结果显示,尽管1 nm-水锰矿相对无定形铁的氧化物/氢氧化物而言是成岩型结核中的优势矿物,但是稀土元素主要富集在无定形铁的氧化物/氢氧化物中.虽然稀土元素在海水中主要是以碳酸盐络合物的形式存在,但是无定形铁的氧化物/氢氧化物则是从海水中获得自由稀土元素离子来络合,而1 nm-水锰矿则直接吸附稀土元素的碳酸盐络合物.因此,无定形铁的氧化物/氢氧化物对稀土元素来说具有比1 nm-水锰矿更强的络合能力.成岩型结核的Ce负异常是由于成岩型结核形成于缺氧微环境中,该环境不能把可溶性的Ce~(3+)氧化成不溶性的Ce~(4+)发生沉淀.     

Minor and rare elements in manganese crusts and nodules and sediments from the Manihiki plateau and adjacent areas: Results of HMNZS Tui cruises

Six manganese crusts, 13 manganese nodules, and 16 sediments were analyzed by instrumental neutron activation analysis. Data were generated on selected major and minor elements but geochemical evaluations are based only on Fe, Sc, U, Th, and the rare earth elements (REE). Manganese crusts and manganese nodules have comparable trivalent REE contents and show a shale‐like distribution pattern. Both crusts and nodules are characterized by a positive Ce anomaly but the anomaly is higher in nodules. REE contents in manganese nodules show a linear dependence on the Fe content, and it is concluded that these elements are incorporated in the Fe‐rich (δ‐MnO₂) phase. In the crusts, the REE correlate with Sc and are therefore assumed to be associated with the clay minerals. Uranium contents are significantly higher in the crusts than in nodules whereas Th is slightly higher in the nodules. There is a clear positive correlation between U and Th in nodules but there are too few data to make a similar conclusion for crusts. Compositional data suggest a division of the sediments into two groups. The carbonate sediments have much lower REE contents and a more pronounced negative Ce anomaly than the clays, while both show a lithogenous component as indicated by a slight negative Eu anomaly.     

Distribution des terres rares dans les fractions de sediments et nodules de Fe et Mn associes en l'ocean Indien

The REE distribution in size fractions of sediments and associated ferromanganese nodules from the Indian Ocean was studied. Bulk-sample patterns of sediments result from the combination of coarsest fractions depleted in Ce and fine fractions enriched in Ce. Ce depletion of the coarsest fractions is related to biogenic silica; on the contrary, REE distribution patterns of fine fractions are closely similar to those of associated ferromanganese nodules. The Ce excess in fine fractions is probably of continental origin, but it could also be derived from submarine weathering of volcanic glass or related to Ce oxydation in the marine environment. In fine fractions Ce is probably in its tetravalent state, hence it can easily be scavenged by fine clays and oxyhydroxydes. Trivalent REE can be incorporated in nodules, partly by occlusion of fine clays or oxyhydroxydes and partly by surface to surface transfer as was proposed by Ehrlich (1968). Comparison between REE patterns of fine-sized fractions, nodules and seawater also supported adsorption as a possible mechanism governing the incorporation of REE of sediments and nodules from seawater. Light REE are probably incorporated as oxyhydroxyde complexes, whereas heavy REE are markedly fractionated with increasing atomic number. This fractionation reflects the complexed form of the heavy REE in seawater.     

Ferromanganese Nodules and their Associated Sediments from the Central Indian Ocean Basin: Rare Earth Element Geochemistry

The rare earth element (REE) distribution in nine deep-sea ferromanganese nodules and their associated siliceous sediments from the Central Indian Ocean Basin (CIOB) have been studied to elucidate the REE relationship among them. Total REE concentration varies from 398-928 ppm in the nodules and 137-235 ppm in the associated sediments, suggesting two- to four-fold enrichment in the nodules compared to associated sediments. REE of nodules and their associated sediments show a positive correlation, suggesting REE are supplied from a common source such as seawater. The positive correlation between REE of nodules and sediments from the CIOB is contrary to the competitive scavenging of REE between nodules and sediment in the equatorial Pacific Ocean. REEs in the nodules are carried by Fe, P, and Ti, whereas in the sediment they are carried by P and Mn phases. A similar REE fractionation pattern with middle REE enrichment over heavy and light REE in both the nodules and their associated sediment suggest fractionation is independent of REE abundance and their carrier phases.     

Ferromanganese Nodules and their Associated Sediments from the Central Indian Ocean Basin: Rare Earth Element Geochemistry

Abstract

The rare earth element (REE) distribution in nine deep-sea ferromanganese nodules and their associated siliceous sediments from the Central Indian Ocean Basin (CIOB) have been studied to elucidate the REE relationship among them. Total REE concentration varies from 398–928 ppm in the nodules and 137–235 ppm in the associated sediments, suggesting two- to four-fold enrichment in the nodules compared to associated sediments. REE of nodules and their associated sediments show a positive correlation, suggesting REE are supplied from a common source such as seawater. The positive correlation between REE of nodules and sediments from the CIOB is contrary to the competitive scavenging of REE between nodules and sediment in the equatorial Pacific Ocean. REEs in the nodules are carried by Fe, P, and Ti, whereas in the sediment they are carried by P and Mn phases. A similar REE fractionation pattern with middle REE enrichment over heavy and light REE in both the nodules and their associated sediment suggest fractionation is independent of REE abundance and their carrier phases.     

南海铁锰结核(壳)的稀土元素地球化学

于1987年5—6月间,中、西德在南海进行地球科学调查,获得5个铁锰结壳、6个铁锰结核样品。本文在利用X荧光法测定15个稀土元素的基础上,对南海铁锰结核(壳)的稀土丰度、配分模式与伴生元素的关系以及稀土的来源作了较为详细的探讨。研究表明,南海铁锰结核(壳)的平均丰度为1625×10~(-6),铁锰结核为2167×10~(-6),分别要比太平洋结核高1—2倍,比太平洋北部沉积物高3—4倍,比南海沉积物高10—20倍;结核和结壳的稀土经球粒陨石标准化后的配分模式基本相同,Ce正异常,Eu亏损不明显;与伴生元素、沉积物及岩石稀土对比研究表明,结核(壳)中稀土主要来自南海中酸性岩类风化、淋漓后缓慢沉积。     

中印度洋海盆富稀土沉积地球化学特征及富集机制研究

本文对中印度洋海盆深海富稀土沉积区两根柱样GC02和GC06开展了沉积物涂片观察,X-射线衍射分析,主量、微量和稀土元素分析,以及单矿物原位微区地球化学分析等,探讨了其地球化学特征、物质来源及稀土元素（REY）的富集机制。结果表明,GC02柱状沉积物类型为钙质黏土和沸石黏土,GC06柱状沉积物类型为钙质黏土、含沸石黏土和沸石黏土。稀土元素主要在含沸石黏土和沸石黏土中富集。北美页岩标准化（NASC）配分模式指示沉积物的REY主要来源于海水,矿物学和地球化学等特征表明该地区沉积物陆源组分可能主要源于澳大利亚的风尘物质。元素相关性和CaO/P₂O₅比值等指示了深海富稀土沉积中REY的主要赋存矿物为生物磷灰石（鱼牙/骨等）,其次为铁锰微结核。本文总结和探讨了深海富稀土沉积的形成机制,完善了深海富稀土沉积形成过程的概念模型。     

东太平洋海隆13°N表层含金属沉积物物质组成与元素赋存状态

为了解不同类型含金属沉积物在物质组成和元素赋存状态的差异,对东太平洋海隆13°N洋中脊两侧表层含金属沉积物(站号:E271和E53)进行了矿物学、地球化学分析,顺序提取实验,并与前人对轴部表层沉积物(站号:17A-EPR-TVG1)的研究结果作了对比分析。研究结果表明, E271和E53是远端含金属沉积物,由非浮力热液羽状流中颗粒物沉降所形成的;17A-EPR-TVG1沉积物是近喷口含金属沉积物,由黑烟囱或者热液硫化物丘状体崩塌、堆积,或者由热液羽状流中Fe-Mn氧化物和硫化物快速沉淀而形成的,近喷口沉积物比远端沉积物更富集Fe、Cu和Zn等元素。元素在两种含金属沉积物中的赋存状态基本相同,除了Fe,Cu,Zn,Mo和稀土元素(REE)等元素在远端沉积物中主要存在于Fe-Mn氧化物相,在近喷口沉积物中主要在残留相中。远端沉积物中REE页岩标准化配分模式与海水相似,表明REE主要来自海水,而近喷口沉积物中REE配分模式与热液流体相似,说明REE以高温热液流体来源为主。相关研究结果加深了对热液沉积作用研究的认识。     

海南岛三亚小东海岸礁礁坪沉积物的稀土元素分布特征

对海南岛三亚小东海东北岸礁礁坪表面沉积物的稀土元素进行了分析,结果表明,沉积物的∑REE为80.22mg/kg,稀土元素含量球粒陨石标准化分布模式呈现轻稀土富集、重稀土亏损,Eu明显负异常(0.58),Ce无异常,Y/Ho低(27.60)的陆相模式特征.根据小东海礁坪沉积样品稀土元素的空间分布情况可以推测出礁坪珊瑚表面...     

Sediment geochemistry in coastal maritime Antarctica (Admiralty Bay, King George Island): Evidence from rare earths and other elements

We report the concentrations of 22 elements in short coastal sediment cores of Admiralty Bay (King George Island, Antarctica) determined by Neutron Activation Analysis. We focus the discussion on rare earth elements (REE) because their fractionation patterns in sediments relative to local sources may offer insights about weathering, transportation, deposition, and diagenetic processes. We found strong correlations between REE and Th, indicating detrital origin. Despite strong Eh gradients, the Th-normalized redox-sensitive elements (e.g., Eu, Ce, Fe, As, and others) showed little variability within the sedimentary environment. The exceptions were U (depleted in the upper few centimeters) and Br (enriched in the upper few centimeters). While U appears to be removed from seawater via uptake across the boundary of reducing sediments, the mechanisms driving Br accumulation are unclear, but perhaps related to increasing diatom production driven by regional warming. A comparison with published concentrations from rocks representing the regional eroding units showed that the characteristics of source rock could be recognized in the REE fractionation patterns in our sediments. These results imply no significant alteration during weathering and sediment transport in the coastal region of Admiralty Bay and the prevalence of strong periglacial erosion in ice-free areas of maritime Antarctica in spite of the relatively mild regional environmental setting (e.g., high moisture and high temperatures).     

Cerium anomaly variations in ferromanganese nodules and crusts from the Indian Ocean

Fifty analyses of rare earth elements as well as mineralogical studies have been carried out on a suite of manganese nodules and crusts from the Central Indian Basin and the Western Indian Ocean. The aim was to identify the processes controlling the REE patterns of the phases hosting the REE in the manganese nodules, with an emphasis on an understanding of the Ce anomaly. This has involved separating the encrusting layers and nuclei physically as well as Fe-Mn oxides from the aluminosilicate phase chemically (using a 2 M HCl leach) prior to analysis.

The presence of nodule nuclei seems to have little influence (mostly <5% to a maximum of 30%) on the overall magnitude of the Ce anomalies in these nodules. The ratios of concentrations of elements in the acid leachates and the corresponding bulk values yield flat REE patterns indicating that the aluminosilicate phase contributes very little to the Ce anomalies. Interelement relations indicate that the Ce anomalies are largely controlled by the amorphous mineral phase FeOOH.xH₂O. The relationship of Fe, Ce anomaly and δ-MnO₂ further suggests that Ce is chemisorbed onto iron oxyhydroxides which are epitaxially intergrown with δ-MnO₂.

The regional distribution of the Ce anomaly values appears to depend on many of the factors responsible for the uptake of other minor metals in nodules and crusts.     

REE distribution in water-sediment interface system at deep ocean floor

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Rare earth elements and yttrium in ferromanganese deposits from the South China Sea: distribution, composition and resource considerations

Ferromanganese nodules and crusts contain relatively high concentration of rare earth elements(REE) and yttrium(REY),with a growing interest in exploitation as an alternative to land-based REY resources.On the basis of comprehensive geochemical approach,the abundance and distribution of REY in the ferromanganese nodules from the South China Sea are analyzed.The results indicate that the REY contents in ferromanganese deposits show a clear geographic regularity.Total REY contents range from 69.1×10~(–6) to 2 919.4×10~(–6),with an average value of 1 459.5×10~(–6).Especially,the enrichment rate of Ce content is high,accounting for almost 60% of the total REY.This REE enrichment is controlled mainly by the sorption of ferromanganese oxides and clay minerals in the nodules and crusts.Moreover,the total REY are higher in ferromanganese deposits of hydrogenous origin than of diagenetic origin.Finally,Light REE(LREE) and heavy REE(HREE) oxides of the ferromanganese deposits in the study area can be classified into four grades: non-enriched type,weakly enriched type,enriched type,and extremely enriched type.According to the classification criteria of rare earth resources,the Xisha and Zhongsha platform-central deep basin areas show a great potential for these rare earth metals.     

冲绳海槽中段沉积物物源识别及其热液活动指示

冲绳海槽中段热液活动区表层沉积物的主、微量和稀土元素分析结果表明:区内沉积物主要由陆源物质与热液源物质组分组成,Hg、Au、Sb、Cu、Pb、Zn、Ba、As、Fe和Co等微量元素富集;沉积物的化学风化程度中等,A-CN-K图解表明其暂未受到钾交代影响,且其母岩成分接近花岗闪长岩;北美页岩标准化稀土配分模式曲线整体较为平坦,轻重稀土分馏较弱,部分样品具有与热液流体类似的明显正铕异常.受热液活动影响,部分沉积物中的Fe、Cu、As、Pb和Zn显著富集,结合样品所处站位,整体显示含金属沉积物-过渡沉积物-正常沉积物的空间分配模式.结合(La/Sm)N、(La/Yb)N比值指示区内沉积物的陆源物质主要来自于黄河与台湾岛河流.     

马来半岛彭亨河和吉兰丹河沉积物稀土元素特征及其物源示踪

通过对马来半岛东部彭亨河28个站位和吉兰丹河22个站位表层沉积物进行稀土元素（REE）测试，对比分析了稀土元素的组成特征和分布规律，探讨了稀土元素组成的控制因素和物源示踪意义。结果表明，彭亨河沉积物稀土元素含量介于24.88～304.29 μg/g之间，平均含量为165.22 μg/g，吉兰丹河沉积物中稀土元素含量介于126.02～281.40 μg/g之间，平均值为181.15 μg/g。彭亨河大部分沉积物上陆壳(UCC)标准化模式为重稀土相对轻稀土富集，吉兰丹河沉积物轻重稀土无明显分异。沉积物源岩和矿物组成对两条河流的REE组成起到了重要的控制作用，化学风化对彭亨河REE组成的影响大于吉兰丹河，而彭亨河沉积物粒度组成显著差异也导致了其REE含量变化范围更大。δEu_UCC-(Gd/Yb)_UCC关系图中彭亨河和吉兰丹河沉积物分区明显，表明其可作为定性判别两条河流来源的有效指标，并可用于海区沉积物来源的示踪和定量识别。     

庙岛群岛西部海域表层沉积物常量和稀土元素的分布特征及其物源指示意义

通过对庙岛群岛西部海域表层沉积物常量、稀土元素的系统研究,探讨了表层沉积物元素地球化学特征、控制因素及其物质来源。结果表明,庙岛群岛西部海域表层沉积物常量元素以SiO₂和A1₂O₃为主,SiO₂含量随着沉积物粒径变粗逐渐增大,Al₂O₃含量随着沉积物粒径变细逐渐增大。稀土元素(Rare Earth Element,REE)呈现轻稀土元素(Light Rare Earth Element,LREE)富集、重稀土元素(Heavy Rare Earth Element,HREE)平坦以及中等程度的Eu负异常等特征,轻重稀土分异明显,稀土元素球粒陨石配分曲线与黄河沉积物类似。通过因子分析和相关性分析发现研究区沉积物的元素含量主要取决于陆源碎屑,海洋生物沉积和化学作用对沉积物元素含量有一定的影响,元素含量基本服从粒度控制规律。物源判别结果显示,庙岛群岛西部海域沉积物主要来源于黄河物质和辽河物质,并且从南到北辽河物质的混合比例逐渐升高,黄河物质的混合比例逐渐降低。     

南黄海西部陆架区表层沉积物稀土元素及其物源分析

对南黄海西部陆架区486个表层沉积物样品的稀土元素进行了测试分析。结果表明:稀土元素总量分布特征受粒度影响,其含量总体上随平均粒径的减小而升高,但在局部站位其含量还可能受矿物控制。稀土元素相关参数,如轻重稀土元素分异度、铈异常以及铕异常基本不受粒度影响,而主要受源岩组分控制,可以进行有效的物源判别。研究区不同站位沉积物中稀土元素配分曲线均为右倾的负斜率模式,相对富集轻稀土元素,显示中等程度的铕负异常,无明显铈异常。稀土元素相关参数物源判别表明研究区物质主要来源于黄河。     

东海陆架HY126EA1孔沉积物稀土元素地球化学

HY126EA1孔沉积物稀土元素总量(∑REE)变化范围不大,分布范围为123.45～187.12μg/g,平均值为164.07μg/g,接近于全球沉积物平均稀土元素含量(150～300μg/g)的下限,高于黄海、东海表层沉积物的平均含量,低于渤海、南海表层沉积物的平均含量.各类沉积物以及不同时期同类沉积物的稀土元素标准化曲线的变化趋势非常一致,表明这些沉积物具有相同的物源区.∑REE,δEu和δCe在垂向上具有明显变化,反映了沉积物源区气候环境的阶段性变化.     

Rare earth elements in the phosphatic-enriched sediment of the Peru shelf

Apatite-enriched materials from the Peru shelf have been analyzed for their major oxide and rare earth element (REE) concentrations. The samples consist of (1) the fine fraction of sediment, mostly clay material, (2) phosphatic pellets and fish debris, which are dispersed throughout the fine-grained sediment, (3) tabular-shaped phosphatic crusts, which occur within the uppermost few centimeters of sediment, and (4) phosphatic nodules, which occur on the seafloor. The bulk REE concentrations of the concretions suggest that these elements are partitioned between the enclosed detrital material and the apatite fraction. Analysis of the fine-grained sediment with which the samples are associated suggested that this detrital fraction in the concretions should have shale REE values; the analysis of the fish debris suggested that the apatite fraction might have seawater values. The seawater contribution of REE's is negligible in the nodules and crust, in which the apatite occurs as a fine-grained interstitial cement. That is, the concentration of REE's and the REE patterns are predominantly a function of the amount of enclosed fine-grained sediment. By contrast, the REE pattern of the pelletal apatite suggests a seawater source and the absolute REE concentrations are relatively high. The REE/P₂O₅ ratios of the apatite fraction of these samples thus vary from approximately zero (in the case of the crust and nodules) to as much as approximately 1.2 × 10⁻³ (in the case of the pellets). The range of this ratio suggests that rather subtle variations in the depositional environment might cause a significant variation in the REE content of this authigenic fraction of the sediment.

Pelletal glauconite was also recovered from one sediment core. Its REE concentrations closely resemble those of the fish debris.