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.     

麦哲伦海山群富钴结壳元素地球化学特征及赋存状态

为探究大洋富钴结壳的元素地球化学特征和赋存状态,以西太平洋麦哲伦海山群5个富钴结壳样品为研究对象,通过X射线衍射法、等离子体发射光谱法、等离子体质谱法及相态分析手段,分析了富钴结壳的矿物组成、主量元素和稀土元素含量。结果表明,富钴结壳样品主要结晶矿物为水羟锰矿,次要矿物包括石英、斜长石和钾长石,同时含有大量非晶态铁氧/氢氧化物。富钴结壳样品中Mn和Fe含量最高, Mn为16.87%～26.55%, Fe为14.34%～18.08%。富钴结壳明显富集稀土元素,其稀土总量为1 287～2 000μg/g,Ce含量为632～946μg/g,约占稀土总量的50%;轻稀土含量为1 037～1 604μg/g,重稀土含量为249～395μg/g,轻稀土元素明显高于重稀土元素。稀土元素配分模式呈现Ce正异常而Eu无异常,具有Ce富集特征。麦哲伦海山群富钴结壳是水成沉积成因,基本没有受到海底热液活动和成岩作用的影响。元素赋存状态与其矿物相密切相关, Na、K、Ca、Mg和Sr主要赋存于碳酸盐相, Mn、Ba、Co和Ni主要赋存于锰氧化物相, Fe、Al、P、Ti、Cu、Pb、V、Zn、Zr和REE主要...     

太平洋徐福海山富钴结壳稀土元素和铂族元素赋存状态研究

利用等离子体发射光谱法、等离子体质谱法以及相态分析手段,对太平洋徐福海山富钴结壳稀土和铂族元素地球化学特征、赋存状态及富集机制进行研究。结果表明,富钴结壳稀土和铂族元素明显富集,其稀土总量为1 842～2 854 μg/g,铂族总量为144～1 180 ng/g,老壳层中稀土和铂族元素含量明显高于新壳层,这可能与老壳层发生磷酸盐化作用有关。轻稀土元素含量明显高于重稀土元素含量,呈现Ce正异常而Eu无异常,具有明显Ce富集特征。铂族元素之间发生了明显分异作用,PPGE含量明显高于IPGE,表现出明显Pt正异常而Pd负异常,具有明显Pt富集而Pd亏损特征。稀土元素赋存状态显示,新壳层中稀土元素主要赋存于铁氧化物相,其富集比例为65.40%～70.05%,老壳层中稀土元素主要赋存于残渣态,富集比例为62.27%～65.77%,这可能与残渣态中磷酸盐有关。铂族元素赋存状态显示,新壳层和老壳层中铂族元素都主要赋存于铁氧化物相,其富集比例为63.66%～69.51%,残渣态(29.20%～34.68%)对铂族元素也有一定的富集能力。富钴结壳稀土和铂族元素的富集推测为铁氧化物胶体粒子的吸附作用,受海水氧化性环境影响,可溶性Ce3+和Pt2+分别被氧化成不溶性Ce4+和Pt4+,沉淀被吸附到铁氧化物相中,从而造成富钴结壳稀土和铂族元素的富集。     

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。     

Mössbauer studies and oxidized manganese ratio in ferromanganese nodules and crusts from the Central Indian Ocean

Ferromanganese nodules from siliceous and pelagic clays and crusts from a seamount in Central Indian Ocean were analyzed for chemical composition, mineralogy, iron oxidation as determined by Mössbauer spectroscopy, and oxidized manganese (O/Mn ratio) by iodometric method. Despite considerable variation in chemical composition (Mn/Fe ratio 1.42 to 7.4) and mineralogy, iron is present solely as Fe (III) in the paramagnetic or superparamagnetic phase. The oxidized manganese ratio showed that 73 to 81% of the manganese is Mn (IV). Mn (II) is detected qualitatively by electron spin resonance spectra in the nodules and crusts from the Central Indian Ocean.     

Mineralogical and geochemical constraints on the origin of ferromanganese crusts from the Rivera Plate (western margin of Mexico)

Marine hydrogenetically precipitated ferromanganese crusts are widespread in the Pacific Ocean. They occur as pavements coating volcanic or sedimentary hard-rock substrates, mainly on the slopes of seamounts, plateaus and hills in ocean basins and continental margins. We studied three ferromanganese crusts from one dredge haul from the Rivera Plate (western margin of Mexico), which are up to 15 mm thick and grow directly on a substrate of pillow basalt fragments. They consist of laminated, botryoidal, porous aggregates mostly of Fe and Mn oxyhydroxides and up to 10% silicates. XRD analysis showed the predominance of poorly crystallized mineral phases in the crusts that include Mn-feroxyhyte and vernadite, and an authigenic smectite-like clay. Detrital minerals probably derive from granodiorites of the eastern wall of the neighboring Middle America Trench. Scattered barite grains occur on the crust surface and suggest plume fall-out derived from hydrothermal vents, although a possible pelagic source cannot be dismissed. Ratios between major (Fe, Mn, Si) and trace (Co, Ni, Cu) elements reveal that such crusts are predominantly hydrogenetic in origin, although they show a hydrothermal influence that increases in the outer layers. Iron contents range from 16.2 to 25.2 wt.%, and manganese from 3.4 to 14.5 wt.%. The Fe/Mn ratio ranges from 1.6 to 7.0. The SiO₂/Al₂O₃ ratio ranges from 4.3 to 6.6, indicating the presence of biogenic silica (radiolarians). The concentrations of copper (up to 383 ppm) and cobalt (up to 534 ppm) are significantly below those of the typical hydrogenetic crusts, whereas Ni (up to 1320 ppm) is about the same or slightly lower. REE normalized profiles and ΣREE values (486 to 732 ppm) match those reported for hydrogenetic crusts, but suggest a hydrothermal contribution for the later crust layers. The inferred crust growth rates using the Co-chronometer (44 and 229 mm/Myr) are higher than those reported for pure hydrogenetic crusts (mostly 1 to 6 mm/Myr), thus indicating an increasing hydrothermal influence. The highest growth rate (229 mm/Myr, corresponding to the outer crust layers) suggests a regional hydrothermal input of iron and manganese to seawater. The intensification of regional submarine hydrothermal activity began about 13,000 yr ago, and may be related to the tectonic activity in the complex junction of the Rivera, Cocos, Pacific and North America plates.     

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.     

Carbon isotopic composition and lattice-bound carbonate of Peru-Chile margin phosphorites

New light-stable carbonate-carbon isotope and lattice-bound CO₂ data from Quaternary Peru-Chile margin phosphatic nodules, crusts and pelletal grains, and from associated dolomicritic concretions, are presented, which provide constraints on the timing and mechanisms of growth of these phases in organic carbon-rich sediments. Comparison of δ¹³C values from carbonate fluorapatite (CFA) nodules and pelletal grains (−4.8 to 0.0‰ and −2.9 to +1.0‰ PDB, respectively) with pore-water total dissolved δ¹³C values from these sediments suggests early authigenic CFA precipitation from pore waters within a few centimeters of the sediment-water interface in association with suboxic to perhaps anoxic microbial degradation of organic matter. In contrast, the dolomicritic cores of nodules recovered from about 12°S display both strongly negative to positive δ¹³C values (−10.8 to +6.1‰) characteristic of formation deeper in the sediments in association with methanogenic and perhaps sulfate reduction microbial processes.

The amount of structural carbonate in CFA suggests that carbonate substitution generally increases as δ¹³C in CFA decreases, a probable consequence of increasing carbonate and accompanying charge-balancing substitutions in the CFA lattice in response to increasing pore-water carbonate ion concentrations with depth below the sediment-water interface. In one buried upward-growing nodule, decreasing CFA δ¹³C and increasing structural CO₂ also correspond to decreasing CFA growth rates. These data suggest that in addition to other constraints such as pore-water phosphorus and fluoride availability, the lower limit of CFA precipitation in suboxic to anoxic sediments may be controlled by lattice poisoning due to excessive dissolved carbonate ion concentrations. In organic-rich Peru-Chile margin sediments this depth threshold appears to be at approximately 5–10 cm below the sediment-water interface where maximum CFA CO₂ contents of about 6 Wt.% occur; in less organic-rich settings, greater depths of precipitation of CFA may be anticipated. Below this relatively shallow depth of CFA precipitation on the Peru shelf, high pore-water alkalinity and associated elevated total dissolved carbon and carbonate ion concentration apparently favor the precipitation of authigenic carbonates.     

西太平洋卡罗琳洋脊CM4海山铁锰结壳矿物学和地球化学特征

2017年8月中国科学院海洋研究所在西太平洋低纬度海区的卡罗琳洋脊CM4海山开展了多学科综合调查,发现该海山山体表面分布着大量的铁锰结壳。本文对该海山的5个铁锰结壳样品进行了矿物学和地球化学研究,利用X射线衍射(XRD)、电感耦合等离子光谱及质谱(ICP-OES、ICP-MS)等测试技术分析了铁锰结壳的矿物组成、主微量元素和稀土元素含量,并进一步探讨了铁锰结壳的成因类型。结果表明,该海山铁锰结壳的矿物组成以水羟锰矿为主,含有少量钡镁锰矿、水钠锰矿、针铁矿、纤铁矿、石英和方解石。该海山铁锰结壳的Mn、Fe、Co、Ni、Cu元素平均含量分别为24.24%、15.14%、0.16%、0.34%、0.01%。与全球各大洋海山区铁锰结壳相比,该海山样品的Cu含量很低。该海山铁锰结壳的稀土元素(REY)含量相对偏低,总体为轻稀土(LREE)富集;稀土(REY)配分模式显示相对平坦的特征,呈明显的Ce正异常,轻微的Y负异常和Ho正异常。样品的矿物组成、元素比值、元素组合等都表明该海山铁锰结壳属于水成成因,未受明显的成岩作用影响。     

A study on the exchange additivity of zinc in solid mixtures in seawater——Ⅱ.Stepwise exchange in δ-MnO2/montmorrillonite mixture

In this study the zinc exchange process and the reason for the non-additive exchange of δ-MnO2/montmorrillonite have been investigated. The results suggest that with pH increasing from 2 to 8, the stepwise exchange of zinc occurs on δ-MnO. and montmorrillonite in their mixture.At low pH zinc ions are bound on δ-MnO2, while at high pH, the exchange on montmorrillonite dominates the surface interaction in the mixture. The study demonstrates that the stepwise exchange and the heterogeneity of the binding sites on δ-MnO2 surface are the reason for the non-additive exchange. It is also shown that when δ-MnO2 amounts to 5 %, zinc exchange on sea sediments is controlled by 8-MnO2.     

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

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南海尖峰海山多金属结壳地球化学

南海尖峰海山多金属结壳富含30多种元素,其锰铁矿物主要由钡镁锰矿,δ-MnO_2和FeOOH·xH_2O组成。与其它海区的结壳相比,尖峰海山结壳富含Cu、Ni、Ba、Zn、Pb等元素,而Co、Ti、稀土元素(REE)、Sr等元素相对较贫。研究表明,HREE亏损,具明显的Ce正异常,较明显的Tb正异常和Yb负异常。这是氧化弱碱性海洋环境所致。结壳是水成作用的产物,它的形成受南海独特的古海洋环境所控制,海底火山热液作用,可能也是影响因素之一。     

过渡金属元素Cu、Co、Ni在铁锰结核(壳)中富集的控制因素

在不同生成环境下生成的铁锰结核(壳)吸收不同的过渡金属元素。在成岩作用形成的铁锰结核中,Cu、Ni主要以锰相形式存在,而Co则以铁相的形式存在;在水成作用形成的铁锰结核(壳)中Cu、Co、Ni均以锰相的形式存在。这些过渡金属元素在成岩作用形成的结核中的存在与铁锰结核(壳)中锰矿物和铁的氧化物、氢氧化物的晶体化学特征密切相关,而在水成作用形成的铁锰结核(壳)中的富集与锰矿物和铁的氧化物、氢氧化物的晶体化。学特征关系不大。同时铁锰结核(壳)中锰矿物和铁的氧化物、氢氧化物又严格地受结核(壳)的生成环境的制约,因此,过渡金属元素Cu、Co、Ni在铁锰结核(壳)中的富集在一定程度上受结核(壳)生成环境的控制。     

Submersible observations of manganese nodule and crust deposits on the Tenpo Seamount,Northwestern Pacific

Pavements of manganese nodules and crusts and outcrops of Miocene limestones were observed on the flanks and flat top of the Tenpo Seamount during three Shinkai 2000 dives. The pre‐Miocene volcano supplied nuclei of volcanic rocks and hydrothermal manganese deposits, and subsequent slow or no sedimentation promoted deposition of abundant hydrogenetic nodules and crusts, mainly on the upper flank of the seamount. Nodule pavements generally cover calcareous sand surface sediments, while crusts cover hard outcrops composed probably of volcanic rocks. The fields of crusts and nodules are sparsely distributed with each other on scales of meters to tens of meters. The on‐site observation suggests the deposits have encountered tectonic and/or mass movements that resulted in unusual occurrences of densely stacked nodules and occasionally the nodules resting directly on crusts or hard substrates. Mineralogical and chemical compositions reveal that for nodules and crusts the encrusting manganese layers of around 1 cm thickness are composed of hydrogenetic vernadite, and diagenetic influence is negligible.     

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.     

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.     

Mechanisms of enrichment of the rarer elements in marine manganese nodules

The rare-earth distribution has been determined in five manganese nodules from a range of marine environments. Manganese nodules from Loch Fyne, Scotland, and the Gulf of Aden are characterized by a low absolute abundance of the rare-earth elements and a low Ce/La ratio compared with deep-sea nodules. This difference is interpreted in terms of the diagenetic remobilization of manganese in the high sedimentation regimes leading to the effective fractionation of manganese from the rare-earth elements and the resultant depletion of the rare earths in nodules from these environments. The mechanism of incorporation of the rare-earth elements into manganese nodules is thought to be either the direct adsorption of these elements from seawater or the scavenging of the elements by colloidal iron oxide prior to their incorporation into the authigenic phase of nodules. There appears to be no evidence for the surface transfer of these elements from inorganic detritus into the authigenic phase of nodules as suggested by previous authors. The distribution of U and Th in the nodules is controlled by factors similar to those controlling the rare-earth abundance in nodules. The higher U/Th ratios in nodules from Loch Fyne and the Gulf of Aden is considered to be due to the preferential reduction of UO₂(CO₃)₃^4? to some lower-valency uranium species such as U₃O₈ in nodules from less oxidizing environments.     

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.     

Comparative mineralogy and geochemistry of hydrothermal iron‐rich crusts from the Pitcairn,Teahitia‐mehetia,and Macdonald hot spot areas of the S. W. pacific

Abstract

Hydrothermal iron‐rich crusts have been recovered from a number of hot spot volcanos including Crough Seamount, Pitcairn Volcanos 2 and 1, Cyana Seamount, Teahitia, Moua Pihaa, and Macdonald Seamount in the S. W. Pacific. Mineralogically, the crusts consists of ferrihydrite with traces of the weathering products of volcanic ash (feldspar, nontronite, pyroxene, and serpentinite). The iron oxyhydroxide phase has a mean particle size of 3–4 nm indicating rapid deposition. Electron microprobe studies have revealed the presence of filamentous iron‐silica deposits within the crusts reflecting the possible bacterial oxidation of iron from the hydrothermal fluids. The crusts display wide variability in composition both between individual sampling stations and between seamounts. Endmember analysis shows that the compositional data can be resolved into three endmembers: a Fe‐rich endmember, a light and heavy rare earth element endmember, and a Ba (barite)‐rich endmember. The Fe‐rich endmember appears to contain very low concentrations of most trace elements. For bulk samples, the composition of the iron‐rich crusts reflects dilution of the iron oxyhydroxide phase by volcanic ash and, to a lesser extent, a hydrogenous component. This is illustrated by the wide variability in SiO₂ (11.1–71.3%) and Mn (0.01–1.21%) contents of the crusts. For iron‐rich crusts containing greater than 40% Fe, the Pitcairn crusts display lower contents of Pb, Ba, Mo, U, Th, As, and rare earth elements (REE) and lower cerium anomalies than those from Teahitia. REE profiles of crusts from each of the hot spot volcanoes are characterized by small negative cerium anomalies but pronounced positive europium anomalies. The low average La/Fe ratios of the crusts from the various seamounts (47–572 X 10^‐6) and positive Eu anomalies of the crusts suggest rapid deposition of the iron oxyhydroxide near the hydrothermal vent. The high Fe/Mn ratio of vent fluids at hot spot volcanoes (8.5–5.6) may account for the formation of these iron‐rich crusts. The present data indicate that there may be differences in the nature of the iron‐rich crusts based on the depth of occurrence. This influences the temperature of the venting hydrothermal fluids and the possibility of occurrence of submarine phreatomagmatic eruptions.     

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.