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.     

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。     

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.     

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.     

Rare earth elements-rich phase and enriching mechanism in sediments from CC area, the Pacific Ocean

Compared to North American shale composition (NASC),REE contents of sediments from the CC area in the Pacific Ocean are obviously high except that cerium has equal content to that of NASC.Three-valence rare earth elements were completely enriched in phosphate-phase and cerium in iron-phase.Rare earth elements in the sediments were originally derived from seawater.During lithigenic and minerogenic processes of metalliferous nodules,three-valence rare earth elements in sediments mobilized and incorporated into sediments as authigenous biogenic-apatite,while cerium had change from Ce³⁺ to Ce⁴⁺ and directly precipitated from seawater and entered metalliferous nodules and caused Ceanomalies in REE pattern in sediments.     

东太平洋海盆430柱沉积物特征与地层

对东太平洋海盆 ４３０ 柱沉积物的组分、古生物、结构构造以及古地磁、铀系等进行研究后, 将沉积物进行分类、命名与分层, 并确定其年代。研究表明, 本柱由下至上的沉积物分别为含沸石粘土、深海粘土、硅质粘土和钙质粘土。该柱中存在 ４ 个沉积间断, 其中在 ３２５ ｃｍ附近层位有一厚约 １０ ｃｍ 的多金属结核层,此界面为中中新世至晚上新世的沉积间断,它在 Ｃ Ｃ区内普遍存在, 持续时间长, 分布范围广。反映此时南极底层流十分强盛, 对东太平洋 Ｃ Ｃ 区的沉积作用和多金属结核形成与发育产生重要的影响。     

胶州湾海水-沉积物界面氮、磷、铁的地球化学特征

对胶州湾底层水溶解氧、总氮、总磷、溶解无机氮、活性磷酸盐、铁及孔隙水中溶解无机氮、磷酸盐、铁和沉积物粒度、有机碳进行了分析。结果显示除铵氮外,孔隙水浓度明显高于底层水中浓度,其中硝酸氮、亚硝酸氮、活性磷酸盐、铁在孔隙水中的浓度分别为在底层水中浓度的17.8、9.3、12.5、7.7倍,暗示孔隙水中的物质可能向上覆水体扩散。在横向上,底层水及孔隙水中硝酸氮、亚硝酸氮、铵氮、活性磷酸盐都呈东岸高西岸低的分布规律,在西南部出现低值。Fe在底层水及孔隙水中的分布规律为东低西高,然而在沉积物中则与此正好相反。氮、磷、铁主要补给源有河流输入、工业生活污染排放、海洋生物自身分解以及孔隙水的释放。影响氮、磷、铁分布的主要因素为物源、河流输入及水动力条件,同时受到沉积物粒度的制约。相关分析显示,溶解氧、有机碳、铁对水体中磷及氮的分布具有某种制约作用。     

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.     

Dynamics of REE accumulation and fractionation in the subcolloidal fraction of bottom sediments in the Razdol’naya River–Amur Bay section,Sea of Japan

The REE contents (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) are determined by atomic emission spectroscopy in the subcolloidal fraction of bottom sediments in the Razdol’naya River–Amur Bay section. The mean contents of lanthanides in soils and river bottom sediments (before the mixing zone) are calculated. The increase in REE content and the fractioning in the series from light to middle and heavy REE in sediments of different estuary zones (river, water mixing, and marine), with the latter related to flocculation, sorption on iron and manganese hydroxides, clay minerals (hydromica, smectites), and lifetime accumulation of marine plankton, are dtermined. Via extraction of 0.5 N sodium hydroxide solution, the content of lanthanides associated with humic substances of subcolloidal fraction from the Amur Bay sediments are determined: 1.3 to 8.2% of La; 1.1 to 11% of Ce; and 0.3 to 1.5 of Gd.     

西北太平洋多金属结核铂族元素地球化学特征

Polymetallic nodules and cobalt (Co)-rich crusts are enriched in platinum-group elements (PGEs),especially platinum (Pt) and may be important sinks of PGEs.At present,little information is available on PGEs in polymetallic nodules,and their geochemical characteristics and the causes of PGEs enrichment are unclear.Here PGEs of polymetallic nodules from abyssal basin in the Marcus-Wake Seamount area of the Northwest Pacific Ocean are reported and compared with the published PGEs data of polymetallic nodules and Co-rich crusts in the Pacific.The total PGEs (ΣPGE) content of polymetallic nodules in study area is 258×10~(–9) in average,markedly higher than that of Clarion-Clipperton Zone (CCZ) nodules (ΣPGE=127×10~(–9)) and lower than that of Co-rich crusts in the Marcus-Wake Seamount (ΣPGE=653×10~(–9)),similar to that of Co-rich crusts in the South China Sea(ΣPGE=252×10~(–9)).The CI chondrite-normalized PGEs patterns in different regions of polymetallic nodules and cobalt-rich crusts are highly consistent,with all being characterized by positive Pt and negative Pd anomalies These results,together with those of previous studies,indicate that PGEs in polymetallic nodules and Co-rich crusts are mainly derived directly from seawater.Pt contents of polymetallic nodules from the study area are negatively correlated with water depth,and Pt/ΣPGE ratios in nodules there are also lower than those of the Corich crusts in the adjacent area,indicating that sedimentary water depth and oxygen fugacity of ambient seawater are the possible important controlling factors for Pt accumulation in crusts and nodules.     

九龙江河口区稀土元素地球化学特征

用电感耦合等离子体质谱（ICP-MS）对2007年10月航次采集的九龙江河口区溶解态、悬浮颗粒态、沉积物样品中的稀土元素（REEs）进行了测定,对REEs的地球化学特征进行研究.结果表明,REEs在各相态中的含量范围如下：溶解态的为0.1 ng/dm^3（Eu）～1.96μg/dm^3（Ce）,悬浮颗粒态的为0.28（Tm）～142.83（Ce）mg/kg,沉积物的为0.25（Tm）～99.65（Ce）mg/kg;溶解态、悬浮颗粒态及沉积物中REEs球粒陨石标准化配分曲线均表现为负斜率型,九龙江河口为LREE相对HREE富集型河口.九龙江河口溶解态、悬浮颗粒态、沉积物三相态中REEs含量受流域土壤、地表径流等源区因素影响较大.Ce异常值在各相态中表现为负异常.     

广东近岸海湾表层沉积物的稀土元素特征及其物源示踪

本文对广东省近岸10个典型海湾的表层沉积物进行了系统的稀土元素(rare earth elements,REE)测试和分析,以期发现沉积物的物源组成特征及其控制因素。研究结果表明,同一海湾内沉积物的稀土丰度差异不明显,但不同海湾之间具有一定的差别(133.58—251.77mg.kg 1)。球粒陨石标准化配分曲线表现出轻稀土(La到Eu)富集、重稀土(Gd到Lu)亏损、δEu负异常等典型的陆源沉积物特征;PAAS(Post-Archean Australian Shale)标准化配分模式显示出明显的中稀土(Sm到Ho)富集特征,与已报道的国内河流沉积物REE特征相似。海湾沉积物与入海河流沉积物及流域内的原岩组成特征的比较说明,后者对海湾沉积物的控制作用明显。REE配分曲线的一致性和中稀土富集特征表明海湾沉积物主要来自汇入海湾的山溪及河流输入的沉积物。     

马里亚纳海沟挑战者深渊初期多金属氧化物的 矿物学、地球化学特征及其成因环境研究

对大洋27航次在西太平洋马里亚纳海沟挑战者深渊获取的3个多金属氧化物样品进行了X射线矿物衍射分析、穆斯堡尔谱分析及地球化学元素分析,研究其矿物、地球化学特征差异。结果表明,所取样品处于多金属氧化物发育的初始阶段,具有独特的矿物地球化学特征:(1)相较于太平洋CC区及中太平洋海盆获取的多金属结核样品,本研究样品的矿物组成中含有异常高的石英、斜长石以及黏土矿物,而水羟锰矿和钙锰矿含量较低。(2)样品中铁相矿物主要为正方针铁矿(91.6%),另含少量纤铁矿(8.4%),推测是纤铁矿向更加稳定的正方针铁矿衍变的结果。(3)由于样品中深海黏土组分以及氧化物核心物质的混入,加上吸附金属氧化物时间较短,导致SiO₂和Al₂O₃含量均高于正常结核,而Fe、Mn、Cu、Co、Ni等其余金属元素含量较低。(4)由于形成时间较短,样品中稀土元素含量相对较低,ΣREE仅约为0.4×10^-3(一般太平洋CC区及中太平洋结核中稀土含量均大于1.0×10^-3);加之海水氧化还原作用的降低以及研究区海底热液活动的影响,Ce元素未表现出多金属结核中常见的正异常。     

太平洋CC区多金属结核成矿元素迁移规律的界面地球化学研究

本文通过对太平洋 Ｃ Ｃ 区东区上覆水、间隙水、沉积物、结核中的环境参数、元素含量进行分析,研究了成矿元素在界面间（上覆水沉积物、间隙水沉积物、上覆水间隙水、沉积物结核）的迁移变化规律,为了解和揭示大洋多金属结核成因及成矿规律提供了依据。     

西太平洋深海沉积物孔隙水稀土元素地球化学特征及意义

为探索深海孔隙水中稀土元素的生物地球化学循环过程,对太平洋菲律宾海九州-帕劳海脊东、西两侧的两个钻孔沉积物进行了高精度的孔隙水采样工作,分析了主、微量元素和稀土元素的地球化学特征,并对稀土元素的浓度、配分模式以及分馏特征进行了详细的讨论。结果表明:这两个钻孔沉积物均处于氧化环境,表现出海水-沉积物界面和浅层孔隙水(2.5~20 cm)中相对富集轻稀土和中稀土,而中层(25~60 cm)和深层沉积物(>65 cm)孔隙水中则相对富集重稀土元素的特征。初步推断有机质和锰(氢)氧化物的分解和吸附作用是造成孔隙水中稀土元素分馏的主要因素。相比于九州-帕劳海脊的东、西两侧海域,孔隙水中的稀土元素浓度和分馏程度存在一定的差异,周围环境中的矿物组成和锰(氢)氧化物等是其主要的控制因素,但是研究区域深海孔隙流体并不能为海洋贡献稀土元素。     

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.     

Distribution of rare earth elements and neodymium isotopes in suspended particles of the tropical Atlantic Ocean (EUMELI site)

We analyzed the REE, Mn and Al concentrations and Nd isotopic ratios in marine suspensions collected on filters (0.65 μm porosity) with in situ pumping systems in the tropical northeastern Atlantic (20°N, 18–31°W). Previously we reported the same parameters on large sinking particles collected with moored sediment traps at the sites. Shale-normalized REE patterns of the filtered suspensions are characterized by a larger light REE (LREE) to heavy REE (HREE) enrichment compared to the trapped material and a Ce anomaly that evolves positively with depth. Depth profiles of REE/Al show maximum values at 50–100 m, where the Mn/Al ratio also reaches a maximum. The profile of the Nd isotopic ratios of the filtered suspensions shows variations similar to those of the seawater. These results suggest that the filtered suspensions preferentially scavenge the LREE, especially Ce, and that the particulate Mn oxides are potential REE carriers. The relationship between the Ce anomaly and the Ce/Al ratio demonstrates that the particulate Ce anomaly is formed by (1) the LREE adsorption onto the particulate Mn oxides in the surface water, (2) Ce(III) oxidation to insoluble Ce(IV)O₂ and (3) preferential desorption of strict trivalent REE from the Mn oxides in deep water. Estimated authigenic Nd contents, using Nd isotopic ratios, decrease with depth. This is consistent with the adsorption of the REE in surface water and their desorption in deep water, suggested by the Ce anomaly formation. All the results show that the suspended particles record more clearly the authigenic REE contribution than the trapped material does. The suspended matter plays a key role in the scavenging of particle-reactive elements.     

太平洋东部CC48孔沉积物稀土元素地球化学研究

研究样品于１９８８年采自太平洋东部ＣＣ４８孔。通过对沉积物稀土元素地球化学特征的分析发现：（１）各种类型深海沉积物的稀土含量有所差别，以稀土元素总量而论，深海粘土＞硅质软泥＞硅钙质软泥＞钙质软泥；沉积物中的自生矿物、硅质生物成因的非晶质ＳｉＯ２及碎屑矿物对稀土元素起富集作用，而生物ＣａＣＯ３则起分散作用。（２）稀土元素含量随深度发生变化。为地层划分提供了依据，应用元素地层学方法将岩芯分成５个层段。     

Rare earth element geochemistry in cold-seep pore waters of Hydrate Ridge, northeast Pacific Ocean

The concentrations of rare earth elements (REEs), sulphate, hydrogen sulphide, total alkalinity, calcium, magnesium and phosphate were measured in shallow (<12 cm below seafloor) pore waters from cold-seep sediments on the northern and southern summits of Hydrate Ridge, offshore Oregon. Downward-decreasing sulphate and coevally increasing sulphide concentrations reveal sulphate reduction as dominant early diagenetic process from ~2 cm depth downwards. A strong increase of total dissolved REE (∑REE) concentrations is evident immediately below the sediment–water interface, which can be related to early diagenetic release of REEs into pore water resulting from the re-mineralization of particulate organic matter. The highest pore water ∑REE concentrations were measured close to the sediment–water interface at ~2 cm depth. Distinct shale-normalized REE patterns point to particulate organic matter and iron oxides as main REE sources in the upper ~2-cm depth interval. In general, the pore waters have shale-normalized patterns reflecting heavy REE (HREE) enrichment, which suggests preferential complexation of HREEs with carbonate ions. Below ~2 cm depth, a downward decrease in ∑REE correlates with a decrease in pore water calcium concentrations. At this depth, the anaerobic oxidation of methane (AOM) coupled to sulphate reduction increases carbonate alkalinity through the production of bicarbonate, which results in the precipitation of carbonate minerals. It seems therefore likely that the REEs and calcium are consumed during vast AOM-induced precipitation of carbonate in shallow Hydrate Ridge sediments. The analysis of pore waters from Hydrate Ridge shed new light on early diagenetic processes at cold seeps, corroborating the great potential of REEs to identify geochemical processes and to constrain environmental conditions.     

Effects of fine grain size on distribution of Mn in shallow and deep water Black Sea sediments: A comparison between oxic and anoxic depositional environments

The uppermost 5–6 cm of the sediments (between 8 and 2248 m water depths) were studied to understand the effects of varying redox conditions on the Mn distribution in the recent sediments of the Black Sea. It was found that most Mn concentrations are consistent with the average abundance in crustal and/or sedimentary rocks. There exist no important differences between Mn concentrations in oxic (shallower water; <70 m) and anoxic (deeper water; 120 m) sediments. Previously reported Mn-enrichment above the Black Sea oxic/anoxic interface, due to the peculiar redox cycling, shows no significant contribution of Mn to the bottom sediments. A marked relationship between total Mn concentrations and clay/mud contents at shelf depth along the southern Black Sea margin indicates increased accumulation of Mn in association with the fine-grained particles and eastward water circulation.